Edge formability in metallic alloys

ABSTRACT

This disclosure is directed at mechanical property improvement in a metallic alloy that has undergone one or more mechanical property losses as a consequence of forming an edge, such as in the formation of an internal hole or an external edge. Methods are disclosed that provide the ability to improve mechanical properties of metallic alloys that have been formed with one or more edges placed in the metallic alloy by a variety of methods which may otherwise serve as a limiting factor for industrial applications.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 16/522,708, filed Jul. 26, 2019, which is a continuation of U.S. patent application Ser. No. 15/438,313 filed Feb. 21, 2017, now U.S. Pat. No. 10,465,260, which is a continuation-in-part of U.S. patent application Ser. No. 15/094,554 filed Apr. 8, 2016, now U.S. Pat. No. 10,480,042, which claims the benefit of U.S. Provisional Patent Application Ser. No. 62/146,048 filed on Apr. 10, 2015 and U.S. Provisional Patent Application Ser. No. 62/257,070 filed on Nov. 18, 2015, all of which are fully incorporated herein by reference.

FIELD OF INVENTION

This disclosure relates to methods for mechanical property improvement in a metallic alloy that has undergone one or more mechanical property losses as a consequence of shearing, such as in the formation of a sheared edge portion or a punched hole. More specifically, methods are disclosed that provide the ability to improve mechanical properties of metallic alloys that have been formed with one or more sheared edges which may otherwise serve as a limiting factor for industrial applications.

BACKGROUND

From ancient tools to modem skyscrapers and automobiles, steel has driven human innovation for hundreds of years. Abundant in the Earth's crust, iron and its associated alloys have provided humanity with solutions to many daunting developmental barriers. From humble beginnings, steel development has progressed considerably within the past two centuries, with new varieties of steel becoming available every few years. These steel alloys can be broken up into three classes based upon measured properties, in particular maximum tensile strain and tensile stress prior to failure. These three classes are: Low Strength Steels (LSS), High Strength Steels (HSS), and Advanced High Strength Steels (AHSS). Low Strength Steels (LSS) are generally classified as exhibiting ultimate tensile strengths less than 270 MPa and include such types as interstitial free and mild steels. High-Strength Steels (HSS) are classified as exhibiting ultimate tensile strengths from 270 to 700 MPa and include such types as high strength low alloy, high strength interstitial free and bake hardenable steels. Advanced High-Strength Steels (AHSS) steels are classified by ultimate tensile strengths greater than 700 MPa and include such types as Martensitic steels (MS), Dual Phase (DP) steels, Transformation Induced Plasticity (TRIP) steels, and Complex Phase (CP) steels. As the strength level increases the trend in maximum tensile elongation (ductility) of the steel is negative, with decreasing elongation at high ultimate tensile strengths. For example, tensile elongation of LSS, HSS and AHSS ranges from 25% to 55%, 10% to 45%, and 4% to 30%, respectively.

Production of steel continues to increase, with a current US production around 100 million tons per year with an estimated value of S75 billion. Steel utilization in vehicles is also high, with advanced high strength steels (AHSS) currently at 17% and forecast to grow by 300% in the coming years [American Iron and Steel Institute. (2013). Profile 2013. Washington, D.C.]. With current market trends and governmental regulations pushing towards higher efficiency in vehicles, AHSS are increasingly being pursued for their ability to provide high strength to mass ratio. The high strength of AHSS allows for a designer to reduce the thickness of a finished part while still maintaining comparable or improved mechanical properties. In reducing the thickness of a part, less mass is needed to attain the same or better mechanical properties for the vehicle thereby improving vehicle fuel efficiency. This allows the designer to improve the fuel efficiency of a vehicle while not compromising on safety.

One key attribute for next generation steels is formability. Formability is the ability of a material to be made into a particular geometry without cracking, rupturing or otherwise undergoing failure. High formability steel provides benefit to a part designer by allowing for the creation of more complex part geometries allowing for reduction in weight. Formability may be further broken into two distinct forms: edge formability and bulk formability. Edge formability is the ability for an edge to be formed into a certain shape. Edges on materials are created through a variety of methods in industrial processes, including but not limited to punching, shearing, piercing, stamping, perforating, cutting, or cropping. Furthermore, the devices used to create these edges are as diverse as the methods, including but not limited to various types of mechanical presses, hydraulic presses, and/or electromagnetic presses. Depending upon the application and material undergoing the operation, the range of speeds for edge creation is also widely varying, with speeds as low as 0.25 mm/s and as high as 3700 mm/s. The wide variety of edge forming methods, devices, and speeds results in a myriad of different edge conditions in use commercially today.

Edges, being free surfaces, are dominated by defects such as cracks or structural changes in the sheet resulting from the creation of the sheet edge. These defects adversely affect the edge formability during forming operations, leading to a decrease in effective ductility at the edge. Bulk formability on the other hand is dominated by the intrinsic ductility, structure, and associated stress state of the metal during the forming operation. Bulk formability is affected primarily by available deformation mechanisms such as dislocations, twinning, and phase transformations. Bulk formability is maximized when these available deformation mechanisms are saturated within the material, with improved bulk formability resulting from an increased number and availability of these mechanisms.

Edge formability can be measured through hole expansion measurements, whereby a hole is made in a sheet and that hole is expanded by means of a conical punch. Previous studies have shown that conventional AHSS materials suffer from reduced edge formability compared with other LSS and HSS when measured by hole expansion [M. S. Billur, T. Altan, “Challenges in forming advanced high strength steels”, Proceedings of New Developments in Sheet Metal Forming, pp. 285-304, 2012]. For example, Dual Phase (DP) steels with ultimate tensile strength of 780 MPa achieve less than 20% hole expansion, whereas Interstitial Free steels (IF) with ultimate tensile strength of approximately 400 MPa achieve around 100% hole expansion ratio. This reduced edge formability complicates adoption of AHSS in automotive applications, despite possessing desirable bulk formability.

SUMMARY

The present invention provides a cold rolled steel sheet product comprising Fe and at least four alloying elements selected from Si, Mn, B, Cr, Ni, Cu and C, wherein the steel sheet product includes a sheared edge, has an ultimate tensile strength of at least 799 MPa, a total elongation of at least 6.6 percent, and a hole expansion ratio greater than 20.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description below may be better understood with reference to the accompanying FIGS. which are provided for illustrative purposes and are not to be considered as limiting any aspect of this invention.

FIG. 1A—Structural pathway for the formation of High Strength Nanomodal Structure and associated mechanisms.

FIG. 1B—Structural pathway for the formation of Recrystallized Modal Structure and Refined High Strength Nanomodal Structure and associated mechanisms.

FIG. 2—Structural pathway toward developing Refined High Strength Nanomodal Structure which is tied to industrial processing steps.

FIG. 3—Images of laboratory cast 50 mm slabs from: a) Alloy 9 and b) Alloy 12.

FIG. 4—Images of hot rolled sheet after laboratory casting from: a) Alloy 9 and b) Alloy 12.

FIG. 5—Images of cold rolled sheet after laboratory casting and hot rolling from: a) Alloy 9 and b) Alloy 12.

FIG. 6—Microstructure of solidified Alloy 1 cast at 50 mm thickness:

-   a) Backscattered SEM micrograph showing the dendritic nature of the     Modal Structure in the as-cast state, b) Bright-field TEM micrograph     showing the details in the matrix grains, c) Bright-field TEM with     selected electron diffraction exhibiting the ferrite phase in the     Modal Structure.

FIG. 7—X-ray diffraction pattern for the Modal Structure in Alloy 1 alloy after solidification: a) Experimental data, b) Rietveld refinement analysis.

FIG. 8—Microstructure of Alloy 1 after hot rolling to 1.7 mm thickness:

-   -   a) Backscattered SEM micrograph showing the homogenized and         refined Nanomodal Structure,     -   b) Bright-field TEM micrograph showing the details in the matrix         grains.

FIG. 9—X-ray diffraction pattern for the Nanomodal Structure in Alloy 1 after hot rolling: a) Experimental data, b) Rietveld refinement analysis.

FIG. 10—Microstructure of Alloy 1 after cold rolling to 1.2 mm thickness:

-   a) Backscattered SEM micrograph showing the High Strength Nanomodal     Structure after cold rolling, b) Bright-field TEM micrograph showing     the details in the matrix grains.

FIG. 11—X-ray diffraction pattern for the High Strength Nanomodal Structure in Alloy 1 after cold rolling: a) Experimental data, b) Rietveld refinement analysis.

FIG. 12—Bright-field TEM micrographs of microstructure in Alloy 1 after hot roiling, cold rolling and annealing at 850° C., for 5 min exhibiting the Recrystallized Modal Structure: a) Low magnification image, b) High magnification image with selected electron diffraction pattern showing crystal structure of austenite phase.

FIG. 13—Backscattered SEM micrographs of microstructure in Alloy 1 after hot rolling, cold rolling and annealing at 850° C. for 5 min exhibiting the Recrystallized Modal Structure: a) Low magnification image, b) High magnification image.

FIG. 14—X-ray diffraction pattern for the Recrystallized Modal Structure in Alloy 1 after annealing: a) Experimental data, b) Rietveld refinement analysis.

FIG. 15—Bright-field TEM micrographs of microstructure in Alloy 1 showing Refined High Strength Nanomodal Structure (Mixed Microconstituent Structure) formed after tensile deformation: a) Large grains of untransformed structure and transformed “pockets” with refined grains; b) Refined structure within a “pocket”.

FIG. 16—Backscattered SEM micrographs of microstructure in Alloy 1 showing Refined High Strength Nanomodal Structure (Mixed Microconstituent Structure): a) Low magnification image, b) High magnification image.

FIG. 17—X-ray diffraction pattern for Refined High Strength Nanomodal Structure in Alloy 1 after cold deformation: a) Experimental data, b) Rietveld refinement analysis.

FIG. 18—Microstructure of solidified Alloy 2 cast at 50 mm thickness:

-   a) Backscattered SEM micrograph showing the dendritic nature of the     Modal Structure in the as-cast state, b) Bright-field TEM micrograph     showing the details in the matrix grains.

FIG. 19—X-ray diffraction pattern for the Modal Structure in Alloy 2 after solidification: a) Experimental data, b) Rietveld refinement analysis.

FIG. 20—Microstructure of Alloy 2 after hot rolling to 1.7 mm thickness:

-   a) Backscattered SEM micrograph showing the homogenized and refined     Nanomodal Structure, -   b) Bright-field TEM micrograph showing the details in the matrix     grains.

FIG. 21—X-ray diffraction pattern for the Nanomodal Structure in Alloy 2 after hot rolling: a) Experimental data, b) Rietveld refinement analysis.

FIG. 22—Microstructure of Alloy 2 after cold rolling to 1.2 mm thickness:

-   a) Backscattered SEM micrograph showing the High Strength Nanomodal     Structure after cold rolling b) Bright-field TEM micrograph showing     the details in the matrix grains.

FIG. 23—X-ray diffraction pattern for the High Strength Nanomodal Structure in Alloy 2 after cold rolling: a) Experimental data, b) Rietveld refinement analysis.

FIG. 24—Bright-field TEM micrographs of microstructure in Alloy 2 after hot rolling, cold rolling and annealing at 850° C. for 10 min exhibiting the Recrystallized Modal Structure: a) Low magnification image, b) High magnification image with selected electron diffraction pattern showing crystal structure of austenite phase.

FIG. 25—Backscattered SEM micrographs of microstructure in Alloy 2 after hot rolling, cold rolling and annealing at 850° C. for 10 min exhibiting the Recrystallized Modal Structure: a) Low magnification image, b) High magnification image.

FIG. 26—X-ray diffraction pattern for the Recrystallized Modal Structure in Alloy 2 after annealing: a) Experimental data, b) Rietveld refinement analysis.

FIG. 27—Microstructure in Alloy 2 showing Refined High Strength Nanomodal Structure (Mixed Microconstituent Structure) formed after tensile deformation: a) Bright-field TEM micrographs of transformed “pockets” with refined grains; b) Back-scattered SEM micrograph of the microstructure.

FIG. 28—X-ray diffraction pattern for Refined High Strength Nanomodal Structure in Alloy 2 after cold deformation: a) Experimental data, b) Rietveld refinement analysis.

FIG. 29—Tensile properties of Alloy 1 at various stages of laboratory processing.

FIG. 30—Tensile results for Alloy 13 at various stages of laboratory processing.

FIG. 31—Tensile results for Alloy 17 at various stages of laboratory processing.

FIG. 32—Tensile properties of the sheet in hot rolled state and after each step of cold rolling/annealing cycles demonstrating full property reversibility at each cycle in: a) Alloy, b) Alloy 2.

FIG. 33—A bend test schematic showing a bending device with two supports and a former (International Organization for Standardization, 2005).

FIG. 34—Images of bend testing samples from Alloy 1 tested to 180°: a) Picture of a full set of samples tested to 180° without cracking, and b) A close-up view of the bend of a tested sample.

FIG. 35—a) Tensile test results of the punched and EDM cut specimens from selected alloys demonstrating property decrease due to punched edge damage, b) Tensile curves of the selected alloys for EDM cut specimens.

FIG. 36—SEM images of the specimen edges in Alloy 1 after a) EDM cutting and b) Punching.

FIG. 37—SEM images of the microstructure near the edge in Alloy 1: a) EDM cut specimens and b) Punched specimens.

FIG. 38—Tensile test results for punched specimens from Alloy 1 before and after annealing demonstrating full property recovery from edge damage by annealing. Data for EDM cut specimens for the same alloy are shown for reference.

FIG. 39—Example tensile stress-strain curves for punched specimens from Alloy 1 with and without annealing.

FIG. 40—Tensile stress-strain curves illustrating the response of cold rolled Alloy 1 to recovery temperatures in the range between 400° C. and 850° C.; a) Tensile curves, b) Yield strength.

FIG. 41—Bright-field TEM images of cold rolled ALLOY 1 samples exhibiting the highly deformed and textured High Strength Nanomodal Structure: a) Lower magnification image, b) Higher magnification image.

FIG. 42—Bright-field TEM images of ALLOY 1 samples annealed at 450° C. 10 min exhibiting the highly deformed and textured High Strength Nanomodal Structure with no recrystallization occurred: a) Lower magnification image, b) Higher magnification image.

FIG. 43—Bright-field TEM images of ALLOY 1 samples annealed at 600° C. 10 min exhibiting nanoscale grains signaling the beginning of recrystallization: a) Lower magnification image, b) Higher magnification image.

FIG. 44—Bright-field TEM images of ALLOY 1 samples annealed at 650° C. 10 min exhibiting larger grains indicating the higher extent of recrystallization: a) Lower magnification image, b) Higher magnification image.

FIG. 45—Bright-field TEM images of ALLOY 1 samples annealed at 700° C. 10 min exhibiting recrystallized grains with a small fraction of untransformed area, and electron diffraction shows the recrystallized grains are austenite: a) Lower magnification image, b) Higher magnification image.

FIG. 46—Model Time Temperature Transformation Diagram representing response of the steel alloys herein to temperature at annealing. In the heating curve labeled A, recovery mechanisms are activated. In the heating curve labeled B, both recovery and recrystallization mechanisms are activated.

FIG. 47—Tensile properties of punched specimens before and after annealing at different temperatures: a) Alloy 1, b) Alloy 9, and c) Alloy 12.

FIG. 48—Schematic illustration of the sample position for structural analysis.

FIG. 49—Alloy 1 punched E8 samples in the as-punched condition: a) Low magnification image showing a triangular deformation zone at the punched edge which is located on the right side of the picture. Additionally close up areas for the subsequent micrographs are provided, b) Higher magnification image showing the deformation zone, c) Higher magnification image showing the recrystallized structure far away from the deformation zone, d) Higher magnification image showing the deformed structure in the deformation zone.

FIG. 50—Alloy 1 punched E8 samples after annealing at 650° C. for 10 min: a) Low magnification image showing the deformation zone at edge, punching in upright direction. Additionally, close up areas for the subsequent micrographs are provided: b) Higher magnification image showing the deformation zone, c) Higher magnification image showing the recrystallized structure far away from the deformation zone, d) Higher magnification image showing the recovered structure in the deformation zone.

FIG. 51—Alloy 1 punched E8 samples after annealing at 700° C. for 10 min: a) Low magnification image showing the deformation zone at edge, punching in upright direction. Additionally, close up areas for the subsequent micrographs are provided, b) Higher magnification image showing the deformation zone, c) Higher magnification image showing the recrystallized structure far away from the deformation zone, d) Higher magnification image showing the recrystallized structure in the deformation zone.

FIG. 52—Tensile properties for specimens punched at varied speeds from: a) Alloy 1, b) Alloy 9, c) Alloy 12.

FIG. 53—HER results for Alloy 1 in a case of punched vs milled hole.

FIG. 54—Cutting plan for SEM microscopy and microhardness measurement samples from HER tested specimens.

FIG. 55—A schematic illustration of microhardness measurement locations.

FIG. 56—Microhardness measurement profile in Alloy 1 HER tested samples with: a) EDM cut and b) Punched holes.

FIG. 57—Microhardness profiles for Alloy 1 in various stages of processing and forming, demonstrating the progression of edge structure transformation during hole punching and expansion.

FIG. 58—Microhardness data for HER tested samples from Alloy 1 with punched and milled holes. Circles indicate a position of the TEM samples in respect to hole edge.

FIG. 59—Bright field TEM image of the microstructure in the Alloy 1 sheet sample before HER testing.

FIG. 60—Bright field TEM micrographs of microstructure in the HER test sample from Alloy 1 with punched hole (HER=5%) at a location of ˜1.5 mm from the hole edge: a) main untransformed structure; b) “pocket” of partially transformed structure.

FIG. 61—Bright field TEM micrographs of microstructure in the HER test sample from Alloy 1 with milled hole (HER=73.6%) at a location of ˜1.5 mm from the hole edge in different areas: a) & b).

FIG. 62—Focused Ion Beam (FIB) technique used for precise sampling near the edge of the punched hole in the Alloy 1 sample: a) FIB technique showing the general sample location of the milled TEM sample, b) Close up view of the cut-out TEM sample with indicated location from the hole edge.

FIG. 63—Bright field TEM micrographs of microstructure in the sample from Alloy 1 with a punched hole at a location of ˜10 micron from the hole edge.

FIG. 64—Hole expansion ratio measurements for Alloy 1 with and without annealing of punched holes.

FIG. 65—Hole expansion ratio measurements for Alloy 9 with and without annealing of punched holes.

FIG. 66—Hole expansion ratio measurements for Alloy 12 with and without annealing of punched holes.

FIG. 67—Hole expansion ratio measurements for Alloy 13 with and without annealing of punched holes.

FIG. 68—Hole expansion ratio measurements for Alloy 17 with and without annealing of punched holes.

FIG. 69—Tensile performance of Alloy 1 tested with different edge conditions. Note that tensile samples with Punched edge condition have reduced tensile performance when compared to tensile samples with wire EDM cut and punched with subsequent annealing (850° C. for 10 minutes) edge conditions.

FIG. 70—Edge foil lability as measured by hole expansion ratio response of Alloy 1 as a function of edge condition. Note that holes in the Punched condition have lower edge formability than holes in the wire EDM cut and punched with subsequent annealing (850° C. for 10 minutes) conditions.

FIG. 71—Punch speed dependence of Alloy 1 edge formability as a function of punch speed, measured by hole expansion ratio. Note the consistent increase in hole expansion ratio with increasing punch speed.

FIG. 72—Punch speed dependence of Alloy 9 edge formability as a function of punch speed, measured by hole expansion ratio. Note the rapid increase in hole expansion ratio up to approximately 25 min/s punch speed followed by a gradual increase in hole expansion ratio.

FIG. 73—Punch speed dependence of Alloy 12 edge formability as a function of punch speed, measured by hole expansion ratio. Note the rapid increase in hole expansion ratio up to approximately 25 mm/s punch speed followed by a continued increase in hole expansion ratio with punch speeds of >100 mm/s.

FIG. 74—Punch speed dependence of commercial Dual Phase 980 steel edge formability measured by hole expansion ratio. Note the hole expansion ratio is consistently 21% with ±3% variance for commercial Dual Phase 980 steel at all punch speeds tested.

FIG. 75—Schematic drawings of non-flat punch geometries: 6° taper (left), 7° conical (center), and conical flat (right). All dimensions are in millimeters.

FIG. 76—Punch geometry effect on Alloy 1 at 28 min/s, 114 mm/s, and 228 mm/s punch speed. Note that for the Alloy 1, the effect of punch geometry diminishes at 228 mm/s punch speed.

FIG. 77—Punch geometry effect on Alloy 9 at 28 mm/s, 114 mm/s, and 228 min/s punch speeds. Note that the 7° conical punch and the conical flat punch result in the highest hole expansion ratio.

FIG. 78—Punch geometry effect on Alloy 12 at 28 mm/s, 114 mm/s, and 228 min/s punch speed. Note that the 7° conical punch results at 228 mm/s punch speed in the highest hole expansion ratio measured for all alloys.

FIG. 79—Punch geometry effect on Alloy 1 at 228 mm/s punch speed. Note that all punch geometries result in nearly equal hole expansion ratios of approximately 21%.

FIG. 80—Hole punch speed dependence of commercial steel grades edge formability measured by hole expansion ratio.

FIG. 81—The post uniform elongation and hole expansion ratio correlation as predicted by [Paul S. K., 3 Mater Eng Perform 2014; 23:3610.] with data for selected commercial steel grades from the same paper along with Alloy 1 and Alloy 9 data.

FIG. 82—The measured hole expansion ratio in samples from Alloy 1 as a function of hole expansion speed.

FIG. 83—The measured hole expansion ratio in samples from Alloy 9 as a function of hole expansion speed.

FIG. 84—The measured hole expansion ratio in samples from Alloy 12 as a function of hole expansion speed.

FIG. 85—Images of the microstructure in the sheet from Alloy 9; a) SEM image of the microstructure, b) Higher magnification SEM image of the microstructure, c) Optical image of the etched surface, and d) Higher magnification optical image of the etched surface.

FIG. 86—The measured hole expansion ratio as a function of hole punching speed and hole expansion speed for sheet of Alloy 9.

FIG. 87—The average magnetic phases volume percent (Fe %) in the HER tested samples with different hole punching speed and hole expansion speed as a function of the distance from the hole edge.

FIG. 88—The measured hole expansion ratio in samples from Alloy 1, Alloy 9, and Alloy 12 as a function of hole preparation method.

FIG. 89—SEM images at low magnification of the cross section near the hole edge in the Alloy 1 samples with holes prepared by different methods prior to expansion; a) Punched hole, b) EDM cut hole, c) Milled hole, and d) Laser cut hole.

FIG. 90—SEM images at high magnification of the cross section near the hole edge in the Alloy 1 samples with holes prepared by different methods prior to expanding at high magnification; a) Punched hole, b) EDM cut hole, c) Milled hole, and d) Laser cut hole.

FIG. 91—SEM images at low magnification of the cross section near the hole edge in the Alloy 1 samples with holes prepared by different methods after expansion during HER testing; a) Punched hole, b) EDM cut hole, c) Milled hole, and d) Laser cut hole.

FIG. 92—SEM images of sample cross sections near the hole edge after HER testing (i.e. after expansion until failure by cracking) are provided at higher magnification for samples from

Alloy 1 with holes prepared by different methods; a) Punched hole, b) EDM cut hole, c) Milled hole, and d) Laser cut hole.

DETAILED DESCRIPTION Structures And Mechanisms

The steel alloys herein undergo a unique pathway of structural formation through specific mechanisms as illustrated in FIG. 1A and FIG. 1B. Initial structure formation begins with melting the alloy and cooling and solidifying and forming an alloy with Modal Structure (Structure #1, FIG. 1A). The Modal Structure exhibits a primarily austenitic matrix (gamma-Fe) which may contain, depending on the specific alloy chemistry, ferrite grains (alpha-Fe), martensite, and precipitates including borides (if boron is present) and/or carbides (if carbon is present). The grain size of the Modal Structure will depend on alloy chemistry and the solidification conditions. For example, thicker as-cast structures (e.g. thickness of greater than or equal to 2.0 mm) result in relatively slower cooling rate (e.g. a cooling rate of less than or equal to 250 K/s) and relatively larger matrix grain size. Thickness may therefore preferably be in the range of 2.0 to 500 mm. The Modal Structure preferably exhibits an austenitic matrix (gamma-Fe) with grain size and/or dendrite length from 2 to 10,000 μm and precipitates at a size of 0.01 to 5.0 μm in laboratory casting. Matrix grain size and precipitate size might be larger, up to a factor of 10 at commercial production depending on alloy chemistry, starting casting thickness and specific processing parameters. Steel alloys herein with the Modal Structure, depending on starting thickness size and the specific alloy chemistry typically exhibits the following tensile properties, yield strength from 144 to 514 MPa, ultimate tensile strength in a range from 411 to 907 MPa, and total ductility from 3.7 to 24.4%.

Steel alloys herein with the Modal Structure (Structure #1, FIG. 1A) can be homogenized and refined through the Nanophase Refinement (Mechanism #1, FIG. 1A) by exposing the steel alloy to one or more cycles of heat and stress ultimately leading to formation of the Nanomodal Structure (Structure #2, FIG. 1A). More specifically, the Modal Structure, when formed at thickness of greater than or equal to 2.0 mm, or formed at a cooling rate of less than or equal to 250 K/s, is preferably heated to a temperature of 700° C. to a temperature below the solidus temperature (Tm) and at strain rates of 10⁻⁶ to 10⁴ with a thickness reduction. Transformation to Structure #2 occurs in a continuous fashion through the intermediate Homogenized Modal Structure (Structure #1a, FIG. 1A) as the steel alloy undergoes mechanical deformation during successive application of temperature and stress and thickness reduction such as what can be configured to occur during hot rolling.

The Nanomodal Structure (Structure #2, FIG. 1A) has a primary austenitic matrix (gamma-Fe) and, depending on chemistry, may additionally contain ferrite grains (alpha-Fe) and/or precipitates such as borides (if boron is present) and/or carbides (if carbon is present). Depending on starting grain size, the Nanomodal Structure typically exhibits a primary austenitic matrix (gamma-Fe) with grain size of 1.0 to 100 μm and/or precipitates at a size 1.0 to 200 nm in laboratory casting. Matrix grain size and precipitate size might be larger up to a factor of 5 at commercial production depending on alloy chemistry, starting casting thickness and specific processing parameters. Steel alloys herein with the Nanomodal Structure typically exhibit the following tensile properties, yield strength from 264 to 574 MPa, ultimate tensile strength in a range from 921 to 1413 MPa, and total ductility from 12.0 to 77.7%. Structure #2 is preferably formed at thickness of 1 mm to 500 mm.

When steel alloys herein with the Nanomodal Structure (Structure #2, FIG. 1A) are subjected to stress at ambient/near ambient temperature (e.g. 25° C. at +/−5° C.), the Dynamic Nanophase Strengthening Mechanism (Mechanism #2, FIG. 1A) is activated leading to formation of the High Strength Nanomodal Structure (Structure #3, FIG. 1A). Preferably, the stress is at a level above the alloy's respective yield strength in a range from 250 to 600 MPa depending on alloy chemistry. The High Strength Nanomodal structure typically exhibits a ferritic matrix (alpha-Fe) which, depending on alloy chemistry, may additionally contain austenite grains (gamma-Fe) and precipitate grains which may include borides (if boron is present) and/or carbides (if carbon is present). Note that the strengthening transformation occurs during strain under applied stress that defines Mechanism #2 as a dynamic process during which the metastable austenitic phase (gamma-Fe) transforms into ferrite (alpha-Fe) with precipitates. Note that depending on the starting chemistry, a fraction of the austenite will be stable and will not transform. Typically, as low as 5 volume percent and as high as 95 volume percent of the matrix will transform. The High Strength Nanomodal Structure typically exhibits a ferritic matrix (alpha-Fe) with matrix grain size of 25 nm to 50 μm and precipitate grains at a size of 1.0 to 200 nm in laboratory casting. Matrix grain size and precipitate size might be larger up to a factor of 2 at commercial production depending on alloy chemistry, starting casting thickness and specific processing parameters. Steel alloys herein with the High Strength Nanomodal Structure typically exhibits the following tensile properties, yield strength from 718 to 1645 MPa, ultimate tensile strength in a range from 1356 to 1831 MPa, and total ductility from 1.6 to 32.8%. Structure #3 is preferably formed at thickness of 0.2 to 25.0 mm.

The High Strength Nanomodal Structure (Structure #3, FIG. 1A and FIG. 1B) has a capability to undergo Recrystallization (Mechanism #3, FIG. 1B) when subjected to heating below the melting point of the alloy with transformation of ferrite grains back into austenite leading to formation of Recrystallized Modal Structure (Structure #4, FIG. 1B). Partial dissolution of nanoscale precipitates also takes place. Presence of borides and/or carbides is possible in the material depending on alloy chemistry. Preferred temperature ranges for a complete transformation occur from 650° C. up to the T_(m) of the specific alloy. When recrystallized, the Structure #4 contains few dislocations or twins and stacking faults can be found in some recrystallized grains. Note that at lower temperatures from 400 to 650° C., recovery mechanisms may occur. The Recrystallized Modal Structure (Structure #4, FIG. 1B) typically exhibits a primary austenitic matrix (gamma-Fe) with grain size of 0.5 to 50 μm and precipitate grains at a size of 1.0 to 200 nm in laboratory casting. Matrix grain size and precipitate size might be larger up to a factor of 2 at commercial production depending on alloy chemistry, starting casting thickness and specific processing parameters. Steel alloys herein with the Recrystallized Modal Structure typically exhibit the following tensile properties: yield strength from 197 to 1372 MPa, ultimate tensile strength in a range from 799 to 1683 MPa, and total ductility from 10.6 to 86.7%.

Steel alloys herein with the Recrystallized Modal Structure (Structure #4, FIG. 1B) undergo Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B) upon stressing above yield at ambient/near ambient temperature (e.g. 25° C. +/−5° C.) that leads to formation of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B). Preferably the stress to initiate Mechanism #4 is at a level above yield strength in a range 197 to 1372 MPa. Similar to Mechanism #2, Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B) is a dynamic process during which the metastable austenitic phase transforms into ferrite with precipitate resulting generally in further grain refinement as compared to Structure #3 for the same alloy. One characteristic feature of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) is that significant refinement occurs during phase transformation in the randomly distributed “pockets” of microstructure while other areas remain untransformed. Note that depending on the starting chemistry, a fraction of the austenite will be stable and the area containing the stabilized austenite will not transform. Typically, as low as 5 volume percent and as high as 95 volume percent of the matrix in the distributed “pockets” will transform. The presence of borides (if boron is present) and/or carbides (if carbon is present) is possible in the material depending on alloy chemistry. The untransformed part of the microstructure is represented by austenitic grains (gamma-Fe) with a size from 0.5 to 50 μm and additionally may contain distributed precipitates with size of 1 to 200 nm. These highly deformed austenitic grains contain a relatively large number of dislocations due to existing dislocation processes occurring during deformation resulting in high fraction of dislocations (10⁸ to 10¹⁰ mm⁻²). The transformed part of the microstructure during deformation is represented by refined ferrite grains (alpha-Fe) with additional precipitate through Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B). The size of refined grains of ferrite (alpha-Fe) varies from 50 to 2000 nm and size of precipitates is in a range from 1 to 200 nm in laboratory casting. Matrix grain size and precipitate size might be larger up to a factor of 2 at commercial production depending on alloy chemistry, starting casting thickness and specific processing parameters. The size of the “pockets” of transformed and highly refined microstructure typically varies from 0.5 to 20 μm. The volume fraction of the transformed vs untransformed areas in the microstructure can be varied by changing the alloy chemistry including austenite stability from typically a 95:5 ratio to 5:95, respectively. Steel alloys herein with the Refined High Strength Nanomodal Structure typically exhibit the following tensile properties: yield strength from 718 to 1645 MPa, ultimate tensile strength in a range from 1356 to 1831 MPa, and total ductility from 1.6 to 32.8%.

Steel alloys herein with the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) may then be exposed to elevated temperatures leading back to formation of a Recrystallized Modal Structure (Structure #4, FIG. 1B). Typical temperature ranges for a complete transformation occur from 650° C. up to the T_(m) of the specific alloy (as illustrated in FIG. 1B) while lower temperatures from 400° C. to temperatures less than 650° C., activate recovery mechanisms and may cause partial recrystallization. Stressing and heating may be repeated multiple times to achieve desired product geometry including but not limited to relatively thin gauges of the sheet, relatively small diameter of the tube or rod, complex shape of final part, etc. with targeted properties. Final thicknesses of the material may therefore fall in the range from 0.2 to 25 mm. Note that cubic precipitates may be present in the steel alloys herein at all stages with a Fm3m (#225) space group. Additional nanoscale precipitates may be formed as a result of deformation through Dynamic Nanophase Strengthening Mechanism (Mechanism #2) and/or Nanophase Refinement & Strengthening (Mechanism #4) that are represented by a dihexagonal pyramidal class hexagonal phase with a P6_(3mc) space group (#186) and/or a ditrigonal dipyramidal class with a hexagonal P6bar2C space group (#190). The precipitate nature and volume fraction depends on the alloy composition and processing history. The size of nanoprecipitates can range from 1 nm to tens of nanometers, but in most cases below 20 nm. Volume fraction of precipitates is generally less than 20%.

Mechanisms During Sheet Production Through Slab Casting

The structures and enabling mechanisms for the steel alloys herein are applicable to commercial production using existing process flows. See FIG. 2. Steel slabs are commonly produced by continuous casting with a multitude of subsequent processing variations to get to the final product form which is commonly coils of sheet. A detailed structural evolution in steel alloys herein from casting to final product with respect to each step of slab processing into sheet product is illustrated in FIG. 2.

The formation of Modal Structure (Structure #1) in steel alloys herein occurs during alloy solidification. The Modal Structure may be preferably formed by heating the alloys herein at temperatures in the range of above their melting point and in a range of 1100° C. to 2000° C. and cooling below the melting temperature of the alloy, which corresponds to preferably cooling in the range of 1×10³ to 1×10⁻³ K/s. The as-cast thickness will be dependent on the production method with Thin Slab Casting typically in the range of 20 to 150 mm in thickness and Thick Slab Casting typically in the range of 150 to 500 mm in thickness. Accordingly, as cast thickness may fall in the range of 20 to 500 mm, and at all values therein, in 1 nun increments. Accordingly, as cast thickness may be 21 mm, 22 mm, 23 mm, etc., up to 500 mm.

Hot rolling of solidified slabs from the alloys is the next processing step with production either of transfer bars in the case of Thick Slab Casting or coils in the case of Thin Slab Casting. During this process, the Modal Structure transforms in a continuous fashion into a partial and then fully Homogenized Modal Structure (Structure #1a) through Nanophase Refinement (Mechanism #1). Once homogenization and resulting refinement is completed, the Nanomodal Structure (Structure #2) forms. The resulting hot band coils which are a product of the hot rolling process is typically in the range of 1 to 20 mm in thickness.

Cold rolling is a widely used method for sheet production that is utilized to achieve targeted thickness for particular applications. For AHSS, thinner gauges are usually targeted in the range of 0.4 to 2 mm. To achieve the finer gauge thicknesses, cold rolling can be applied through multiple passes with or without intermediate annealing between passes. Typical reduction per pass is 5 to 70% depending on the material properties and equipment capability. The number of passes before the intermediate annealing also depends on materials properties and level of strain hardening during cold deformation. For the steel alloys herein, the cold rolling will trigger Dynamic Nanophase Strengthening (Mechanism #2) leading to extensive strain hardening of the resultant sheet and to the formation of the High Strength Nanomodal Structure (Structure #3). The properties of the cold rolled sheet from alloys herein will depend on the alloy chemistry and can be controlled by the cold rolling reduction to yield a fully cold rolled (i.e. hard) product or can be done to yield a range of properties (i.e. ¼, ½, ¾ hard etc.). Depending on the specific process flow, especially starting thickness and the amount of hot rolling gauge reduction, often annealing is needed to recover the ductility of the material to allow for additional cold rolling gauge reduction. Intermediate coils can be annealed by utilizing conventional methods such as batch annealing or continuous annealing lines. The cold deformed High Strength Nanomodal Structure (Structure #3) for the steel alloys herein will undergo Recrystallization (Mechanism #3) during annealing leading to the formation of the Recrystallized Modal Structure (Structure #4). At this stage, the recrystallized coils can be a final product with advanced property combination depending on the alloy chemistry and targeted markets. In a case when even thinner gauges of the sheet are required, recrystallized coils can be subjected to further cold rolling to achieve targeted thickness that can be realized by one or multiple cycles of cold rolling/annealing. Additional cold deformation of the sheet from alloys herein with Recrystallized Modal Structure (Structure 44) leads to structural transformation into Refined High Strength Nanomodal Structure (Structure #5) through Nanophase Refinement and Strengthening (Mechanism #4). As a result, fully hard coils with final gauge and Refined High Strength Nanomodal Structure (Structure #5) can be formed or, in the case of annealing as a last step in the cycle, coils of the sheet with final gauge and Recrystallized Modal Structure (Structure #4) can also be produced. When coils of recrystallized sheet from alloys herein utilized for finished part production by any type of cold deformation such as cold stamping, hydroforming, roll forming etc., Refined High Strength Nanomodal Structure (Structure #5) will be present in the final product/parts. The final products may be in many different forms including sheet, plate, strips, pipes, and tubes and a myriad of complex parts made through various metalworking processes.

Mechanisms for Edge Formability

The cyclic nature of these phase transformations going from Recrystallized Modal Structure (Structure #4) to Refined High Strength Nanomodal Structure (Structure #5) and then back to Recrystallized Modal Structure (Structure #4) is one of the unique phenomenon and features of steel alloys herein. As described earlier, this cyclic feature is applicable during commercial manufacturing of the sheet, especially for AHSS where thinner gauge thicknesses are required (e.g. thickness in the range of 0.2 to 25 mm). Furthermore, these reversibility mechanisms are applicable for the widespread industrial usage of the steel alloys herein. While exhibiting exceptional combinations of bulk sheet formability as is demonstrated by the tensile and bend properties in this application for the steel alloys herein, the unique cycle feature of the phase transformations is enabling for edge formability, which can be a significant limiting factor for other AHSS. Table 1 below provides a summary of the structure and performance features through stressing and heating cycles available through Nanophase Refinement and Strengthening (Mechanism #4). How these structures and mechanisms can be harnessed to produce exceptional combinations of both bulk sheet and edge formability will be subsequently described herein.

TABLE 1 Structures and Performance Through Stressing/Heating Cycles Structure #5 Refined High Strength Structure #4 Nanomodal Structure Recrystallized Transformed Property/Mechanism Modal Structure Untransformed “pockets” Structure Recrystallization Retained austenitic Nanophase Formation occurring at elevated grains Refinement & temperatures in cold Strengthening worked material mechanism occurring through application of mechanical stress in distributed microstructural “pockets” Transformations Recrystallization of cold Precipitation Stress induced deformed iron matrix optional austenite transformation into ferrite and precipitates Enabling Phases Austenite, optionally Austenite, Ferrite, optionally ferrite, precipitates optionally austenite, precipitates precipitates Matrix Grain Size 0.5 to 50 μm 0.5 to 50 μm 50 to 2000 nm Precipitate Size 1 to 200 nm 1 to 200 nm 1 to 200 nm Tensile Actual with properties Actual with properties achieved based on Response achieved based on formation of the structure and fraction of formation of the transformation structure and fraction of transformation Yield Strength 197 to 1372 MPa 718 to 1645 MPa Ultimate Tensile 799 to 1683 MPa 1356 to 1831 MPa Strength Total Elongation 6.6 to 86.7% 1.6 to 32.8%

Main Body

The chemical composition of the alloys herein is shown in Table 2 which provides the preferred atomic ratios utilized.

TABLE 2 Alloy Chemical Composition Alloy Fe Cr Ni Mn Cu B Si C Alloy 1  75.75 2.63 1.19 13.86 0.65 0.00 5.13 0.79 Alloy 2  73.99 2.63 1.19 13.18 1.55 1.54 5.13 0.79 Alloy 3  77.03 2.63 3.79 9.98 0.65 0.00 5.13 0.79 Alloy 4  78.03 2.63 5.79 6.98 0.65 0.00 5.13 0.79 Alloy 5  79.03 2.63 7.79 3.98 0.65 0.00 5.13 0.79 Alloy 6  78.53 2.63 3.79 8.48 0.65 0.00 5.13 0.79 Alloy 7  79.53 2.63 5.79 5.48 0.65 0.00 5.13 0.79 Alloy 8  80.53 2.63 7.79 2.48 0.65 0.00 5.13 0.79 Alloy 9  74.75 2.63 1.19 14.86 0.65 0.00 5.13 0.79 Alloy 10 75.25 2.63 1.69 13.86 0.65 0.00 5.13 0.79 Alloy 11 74.25 2.63 1.69 14.86 0.65 0.00 5.13 0.79 Alloy 12 73.75 2.63 1.19 15.86 0.65 0.00 5.13 0.79 Alloy 13 77.75 2.63 1.19 11.86 0.65 0.00 5.13 0.79 Alloy 14 74.75 2.63 2.19 13.86 0.65 0.00 5.13 0.79 Alloy 15 73.75 2.63 3.19 13.86 0.65 0.00 5.13 0.79 Alloy 16 74.11 2.63 2.19 13.86 1.29 0.00 5.13 0.79 Alloy 17 72.11 2.63 2.19 15.86 1.29 0.00 5.13 0.79 Alloy 18 78.25 2.63 0.69 11.86 0.65 0.00 5.13 0.79 Alloy 19 74.25 2.63 1.19 14.86 1.15 0.00 5.13 0.79 Alloy 20 74.82 2.63 1.50 14.17 0.96 0.00 5.13 0.79 Alloy 21 75.75 1.63 1.19 14.86 0.65 0.00 5.13 0.79 Alloy 22 77.75 2.63 1.19 13.86 0.65 0.00 3.13 0.79 Alloy 23 76.54 2.63 1.19 13.86 0.65 0.00 5.13 0.00 Alloy 24 67.36 10.70 1.25 10.56 1.00 5.00 4.13 0.00 Alloy 25 71.92 5.45 2.10 8.92 1.50 6.09 4.02 0.00 Alloy 26 61.30 18.90 6.80 0.90 0.00 5.50 6.60 0.00 Alloy 27 71.62 4.95 4.10 6.55 2.00 3.76 7.02 0.00 Alloy 28 62.88 16.00 3.19 11.36 0.65 0.00 5.13 0.79 Alloy 29 72.50 2.63 0.00 15.86 1.55 1.54 5.13 0.79 Alloy 30 80.19 0.00 0.95 13.28 1.66 2.25 0.88 0.79 Alloy 31 77.65 0.67 0.08 13.09 1.09 0.97 2.73 3.72 Alloy 32 78.54 2.63 1.19 13.86 0.65 0.00 3.13 0.00 Alloy 33 83.14 1.63 8.68 0.00 1.00 4.76 0.00 0.79 Alloy 34 75.30 2.63 1.34 14.01 0.80 0.00 5.13 0.79 Alloy 35 74.85 2.63 1.49 14.16 0.95 0.00 5.13 0.79

As can be seen from the above, the alloys herein are iron based metal alloys, having greater than or equal to 50 at. % Fe. More preferably, the alloys herein can be described as comprising, consisting essentially of, or consisting of the following elements at the indicated atomic percent: Fe (61.30 to 83.14 at. %); Si (0 to 7.02 at. %); Mn (0 to 15.86 at. %); B (0 to 6.09 at. %); Cr (0 to 18.90 at. %); Ni (0 to 8.68 at. %); Cu (0 to 2.00 at. %); C (0 to 3.72 at. %). In addition, it can be appreciated that the alloys herein are such that they comprise Fe and at least four or more, or five or more, or six or more elements selected from Si, Mn, B, Cr, Ni, Cu or C. Most preferably, the alloys herein are such that they comprise, consist essentially of, or consist of Fe at a level of 50 at. % or greater along with Si, Mn, B, Cr, Ni, Cu and C.

Alloy Laboratory Processing

Laboratory processing of the alloys in Table 2 was done to model each step of industrial production but on a much smaller scale. Key steps in this process include the following: casting, tunnel furnace heating, hot rolling, cold rolling, and annealing.

Casting

Alloys were weighed out into charges ranging from 3,000 to 3,400 grams using commercially available ferroadditive powders with known chemistry and impurity content according to the atomic ratios in Table 2. Charges were loaded into a zirconia coated silica crucibles which was placed into an Indutherm VTC800V vacuum tilt casting machine. The machine then evacuated the casting and melting chambers and backfilled with argon to atmospheric pressure several times prior to casting to prevent oxidation of the melt. The melt was heated with a 14 kHz RF induction coil until fully molten, approximately 5.25 to 6.5 minutes depending on the alloy composition and charge mass. After the last solids were observed to melt it was allowed to heat for an additional 30 to 45 seconds to provide superheat and ensure melt homogeneity. The casting machine then evacuated the melting and casting chambers, tilted the crucible and poured the melt into a 50 mm thick, 75 to 80 mm wide, and 125 mm deep channel in a water cooled copper die. The melt was allowed to cool under vacuum for 200 seconds before the chamber was filled with argon to atmospheric pressure. Example pictures of laboratory cast slabs from two different alloys are shown in FIG. 3.

Tunnel Furnace Heating

Prior to hot rolling, laboratory slabs were loaded into a Lucifer EHS3GT-B18 furnace to heat. The furnace set point varies between 1100° C. to 1250° C. depending on alloy melting point. The slabs were allowed to soak for 40 minutes prior to hot rolling to ensure they reach the target temperature. Between hot rolling passes the slabs are returned to the furnace for 4 minutes to allow the slabs to reheat.

Hot Rolling

Pre-heated slabs were pushed out of the tunnel furnace into a Fenn Model 061 2 high rolling mill. The 50 mm slabs were preferably hot rolled for 5 to 8 passes though the mill before being allowed to air cool. After the initial passes each slab had been reduced between 80 to 85% to a final thickness of between 7.5 and 10 mm. After cooling each resultant sheet was sectioned and the bottom 190 mm was hot rolled for an additional 3 to 4 passes through the mill, further reducing the plate between 72 to 84% to a final thickness of between 1.6 and 2.1 mm. Example pictures of laboratory cast slabs from two different alloys after hot rolling are shown in FIG. 4.

Cold Rolling

After hot rolling resultant sheets were media blasted with aluminum oxide to remove the mill scale and were then cold rolled on a Fenn Model 061 2 high rolling mill. Cold rolling takes multiple passes to reduce the thickness of the sheet to a targeted thickness of typically 1.2 mm. Hot rolled sheets were fed into the mill at steadily decreasing roll gaps until the minimum gap is reached. If the material has not yet hit the gauge target, additional passes at the minimum gap were used until 1.2 mm thickness was achieved. A large number of passes were applied due to limitations of laboratory mill capability. Example pictures of cold rolled sheets from two different alloys are shown in FIG. 5.

Annealing

After cold rolling, tensile specimens were cut from the cold rolled sheet via wire electrical discharge machining (EDM). These specimens were then annealed with different parameters listed in Table 3. Annealing 1a, 1b, 2b were conducted in a Lucifer 7HT-K12 box furnace. Annealing 2a and 3 was conducted in a Camco Model G-ATM-12FL furnace. Specimens which were air normalized were removed from the furnace at the end of the cycle and allowed to cool to room temperature in air. For the furnace cooled specimens, at the end of the annealing the furnace was shut off to allow the sample to cool with the furnace. Note that the heat treatments were selected for demonstration but were not intended to be limiting in scope. High temperature treatments up to just below the melting points for each alloy are possible.

TABLE 3 Annealing Parameters Anneal- ing Heating Temperature Dwell Cooling Atmosphere 1a Preheated  850° C.  5 min Air Air + Argon Furnace Normalized 1b Preheated  850° C.  10 min Air Air + Argon Furnace Normalized 2a 20° C./hr  850° C. 360 min 45° C./hr to Hydrogen + 500° C. then Argon Furnace Cool 2b 20° C./hr  850° C. 360 min 45° C./hr to Air + Argon 500° C. then Air Normalized 3 20° C./hr 1200° C. 120 min Furnace Cool Hydrogen + Argon

Alloy Properties

Thermal analysis of the alloys herein was performed on as-solidified cast slabs using a Netzsch Pegasus 404 Differential Scanning calorimeter (DSC). Samples of alloys were loaded into alumina crucibles which were then loaded into the DSC. The DSC then evacuated the chamber and backfilled with argon to atmospheric pressure. A constant purge of argon was then started, and a zirconium getter was installed in the gas flow path to further reduce the amount of oxygen in the system. The samples were heated until completely molten, cooled until completely solidified, then reheated at 10° C./min through melting. Measurements of the solidus, liquidus, and peak temperatures were taken from the second melting in order to ensure a representative measurement of the material in an equilibrium state. In the alloys listed in Table 2, melting occurs in one or multiple stages with initial melting from ˜1111° C. depending on alloy chemistry and final melting temperature up to ˜1476° C. (Table 4). Variations in melting behavior reflect complex phase formation at solidification of the alloys depending on their chemistry.

TABLE 4 Differential Thermal Analysis Data for Melting Behavior Solidus Liquidus Melting Melting Melting Temperature Temperature Peak #1 Peak #2 Peak #3 Alloy (° C.) (° C.) (° C.) (° C.) (° C.) Alloy 1 1390 1448 1439 Alloy 2 1157 1410 1177 1401 Alloy 3 1411 1454 1451 Alloy 4 1400 1460 1455 Alloy 5 1415 1467 1464 Alloy 6 1416 1462 1458 Alloy 7 1421 1467 1464 Alloy 8 1417 1469 1467 Alloy 9 1385 1446 1441 Alloy 10 1383 1442 1437 Alloy 11 1384 1445 1442 Alloy 12 1385 1443 1435 Alloy 13 1401 1459 1451 Alloy 14 1385 1445 1442 Alloy 15 1386 1448 1441 Alloy 16 1384 1439 1435 Alloy 17 1376 1442 1435 Alloy 18 1395 1456 1431 1449 1453 Alloy 19 1385 1437 1432 Alloy 20 1374 1439 1436 Alloy 21 1391 1442 1438 Alloy 22 1408 1461 1458 Alloy 23 1403 1452 1434 1448 Alloy 24 1219 1349 1246 1314 1336 Alloy 25 1186 1335 1212 1319 Alloy 26 1246 1327 1268 1317 Alloy 27 1179 1355 1202 1344 Alloy 28 1158 1402 1176 1396 Alloy 29 1159 1448 1168 1439 Alloy 30 1111 1403 1120 1397 Alloy 31 1436 1475 1464 Alloy 32 1436 1476 1464 Alloy 33 1153 1418 1178 1411 Alloy 34 1397 1448 1445 Alloy 35 1394 1444 1441

The density of the alloys was measured on 9 mm thick sections of hot rolled material using the Archimedes method in a specially constructed balance allowing weighing in both air and distilled water. The density of each alloy is tabulated in Table 5 and was found to be in the range from 7.57 to 7.89 g/cm³. The accuracy of this technique is ±0.01 g/cm³.

TABLE 5 Density of Alloys Density Alloy (g/cm³) Alloy 1 7.78 Alloy 2 7.74 Alloy 3 7.82 Alloy 4 7.84 Alloy 5 7.76 Alloy 6 7.83 Alloy 7 7.79 Alloy 8 7.71 Alloy 9 7.77 Alloy 10 7.78 Alloy 11 7.77 Alloy 12 7.77 Alloy 13 7.80 Alloy 14 7.78 Alloy 15 7.79 Alloy 16 7.79 Alloy 17 7.77 Alloy 18 7.79 Alloy 19 7.77 Alloy 20 7.78 Alloy 21 7.78 Alloy 22 7.87 Alloy 23 7.81 Alloy 24 7.67 Alloy 25 7.71 Alloy 26 7.57 Alloy 27 7.67 Alloy 28 7.73 Alloy 29 7.89 Alloy 30 7.78 Alloy 31 7.89 Alloy 32 7.89 Alloy 33 7.78 Alloy 34 7.77 Alloy 35 7.78

Tensile properties were measured on an Instron 3369 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s. Strain data was collected using Instron's Advanced Video Extensometer. Tensile properties of the alloys listed in Table 2 after annealing with parameters listed in Table 3 are shown below in Table 6 to Table 10. The ultimate tensile strength values may vary from 799 to 1683 MPa with tensile elongation from 6.6 to 86.7%. The yield strength is in a range from 197 to 978 MPa. The mechanical characteristic values in the steel alloys herein will depend on alloy chemistry and processing conditions. The variation in heat treatment additionally illustrates the property variations possible through processing a particular alloy chemistry.

TABLE 6 Tensile Data for Selected Alloys after Heat Treatment 1a Ultimate Yield Tensile Tensile Strength Strength Elongation Alloy (MPa) (MPa) (%) Alloy 1 443 1212 51.1 458 1231 57.9 422 1200 51.9 Alloy 2 484 1278 48.3 485 1264 45.5 479 1261 48.7 Alloy 3 458 1359 43.9 428 1358 43.7 462 1373 44.0 Alloy 4 367 1389 36.4 374 1403 39.1 364 1396 32.1 Alloy 5 510 1550 16.5 786 1547 18.1 555 1552 16.2 Alloy 6 418 1486 34.3 419 1475 35.2 430 1490 37.3 Alloy 7 468 1548 20.2 481 1567 20.3 482 1545 19.3 Alloy 8 851 1664 13.6 848 1683 14.0 859 1652 12.9 Alloy 9 490 1184 58.0 496 1166 59.1 493 1144 56.6 Alloy 10 472 1216 60.5 481 1242 58.7 470 1203 55.9 Alloy 11 496 1158 65.7 498 1155 58.2 509 1154 68.3 Alloy 12 504 1084 48.3 515 1105 70.8 518 1106 66.9 Alloy 13 478 1440 41.4 486 1441 40.7 455 1424 42.0 Alloy 22 455 1239 48.1 466 1227 55.4 460 1237 57.9 Alloy 23 419 1019 48.4 434 1071 48.7 439 1084 47.5 Alloy 28 583 932 61.5 594 937 60.8 577 930 61.0 Alloy 29 481 1116 60.0 481 1132 55.4 486 1122 56.8 Alloy 30 349 1271 42.7 346 1240 36.2 340 1246 42.6 Alloy 31 467 1003 36.0 473 996 29.9 459 988 29.5 Alloy 32 402 1087 44.2 409 1061 46.1 420 1101 44.1

TABLE 7 Tensile Data for Selected Alloys after Heat Treatment 1b Yield Ultimate Tensile Tensile Strength Strength Elongation Alloy (MPa) (MPa) (%) Alloy 1 487 1239 57.5 466 1269 52.5 488 1260 55.8 Alloy 2 438 1232 49.7 431 1228 49.8 431 1231 49.4 Alloy 9 522 1172 62.6 466 1170 61.9 462 1168 61.3 Alloy 12 471 1115 63.3 458 1102 69.3 454 1118 69.1 Alloy 13 452 1408 40.5 435 1416 42.5 432 1396 46.0 Alloy 14 448 1132 64.4 443 1151 60.7 436 1180 54.3 Alloy 15 444 1077 66.9 438 1072 65.3 423 1075 70.5 Alloy 16 433 1084 67.5 432 1072 66.8 423 1071 67.8 Alloy 17 420 946 74.6 421 939 77.0 425 961 74.9 Alloy 19 496 1124 67.4 434 1118 64.8 435 1117 67.4 Alloy 20 434 1154 58.3 457 1188 54.9 448 1187 60.5 Alloy 21 421 1201 54.3 427 1185 59.9 431 1191 47.8 Alloy 24 554 1151 23.5 538 1142 24.3 562 1151 24.3 Alloy 25 500 1274 16.0 502 1271 15.8 483 1280 16.3 Alloy 26 697 1215 20.6 723 1187 21.3 719 1197 21.5 Alloy 27 538 1385 20.6 574 1397 20.9 544 1388 21.8 Alloy 33 978 1592 6.6 896 1596 7.2 953 1619 7.5 Alloy 34 467 1227 56.7 476 1232 52.7 462 1217 51.6 Alloy 35 439 1166 56.3 438 1166 59.0 440 1177 58.3

TABLE 8 Tensile Data for Selected Alloys after Heat Treatment 2a Yield Ultimate Tensile Tensile Strength Strength Elongation Alloy (MPa) (MPa) (%) Alloy 2 367 1174 46.2 369 1193 45.1 367 1179 50.2 Alloy 30 391 1118 55.7 389 1116 60.5 401 1113 59.5 Alloy 32 413 878 17.6 399 925 20.5 384 962 21.0 Alloy 31 301 1133 37.4 281 1125 38.7 287 1122 39.0

TABLE 9 Tensile Data for Selected Alloys after Heat Treatment 2b Yield Ultimate Tensile Tensile Strength Strength Elongation Alloy (MPa) (MPa) (%) Alloy 1 396 1093 31.2 383 1070 30.4 393 1145 34.7 Alloy 2 378 1233 49.4 381 1227 48.3 366 1242 47.7 Alloy 3 388 1371 41.3 389 1388 42.6 Alloy 4 335 1338 21.7 342 1432 30.1 342 1150 17.3 Alloy 5 568 1593 15.2 595 1596 13.1 735 1605 14.6 Alloy 6 399 1283 17.5 355 1483 24.8 386 1471 23.8 Alloy 7 605 1622 16.3 639 1586 15.2 Alloy 8 595 1585 13.6 743 1623 14.1 791 1554 13.9 Alloy 9 381 1125 53.3 430 1111 44.8 369 1144 51.1 Alloy 10 362 1104 37.8 369 1156 43.5 Alloy 11 397 1103 52.4 390 1086 50.9 402 1115 50.4 Alloy 12 358 1055 64.7 360 1067 64.4 354 1060 62.9 Alloy 13 362 982 17.3 368 961 16.3 370 989 17.0 Alloy 14 385 1165 59.0 396 1156 55.5 437 1155 57.9 Alloy 15 357 1056 70.3 354 1046 68.2 358 1060 70.7 Alloy 16 375 1094 67.6 384 1080 63.4 326 1054 65.2 Alloy 17 368 960 77.2 370 955 77.9 358 951 75.9 Alloy 18 326 1136 17.3 338 1192 19.1 327 1202 18.5 Alloy 19 386 1134 64.5 378 1100 60.5 438 1093 52.5 Alloy 20 386 1172 56.2 392 1129 42.0 397 1186 57.8 Alloy 21 363 1141 49.0 Alloy 22 335 1191 45.7 322 1189 41.5 348 1168 34.5 Alloy 23 398 1077 44.3 367 1068 44.8 Alloy 24 476 1149 28.0 482 1154 25.9 495 1145 26.2 Alloy 25 452 1299 16.0 454 1287 15.8 441 1278 15.1 Alloy 26 619 1196 26.6 615 1189 26.2 647 1193 26.1 Alloy 27 459 1417 17.3 461 1410 16.8 457 1410 17.1 Alloy 28 507 879 52.3 498 874 42.5 493 880 44.7 Alloy 32 256 1035 42.3 257 1004 42.1 257 1049 34.8 Alloy 33 830 1494 8.4 862 1521 8.1 877 1519 8.8 Alloy 34 388 1178 59.8 384 1197 57.7 370 1177 59.1 Alloy 35 367 1167 58.5 369 1167 58.4 375 1161 59.7

TABLE 10 Tensile Data for Selected Alloys after Heat Treatment 3 Yield Ultimate Tensile Tensile Strength Strength Elongation Alloy (MPa) (MPa) (%) Alloy 1 238 1142 47.6 233 1117 46.3 239 1145 53.0 Alloy 3 266 1338 38.5 N/A 1301 37.7 N/A 1291 35.6 Alloy 4 N/A 1353 27.7 N/A 1337 26.1 N/A 1369 29.0 Alloy 5 511 1462 12.5 558 1399 10.6 Alloy 6 311 1465 24.6 308 1467 21.8 308 1460 25.0 Alloy 7 727 1502 12.5 639 1474 11.3 685 1520 12.4 Alloy 8 700 1384 12.3 750 1431 13.3 Alloy 9 234 1087 55.0 240 1070 56.4 242 1049 58.3 Alloy 10 229 1073 50.6 228 1082 56.5 229 1077 54.2 Alloy 11 232 1038 63.8 232 1009 62.4 228 999 66.1 Alloy 12 229 979 65.6 228 992 57.5 222 963 66.2 Alloy 13 277 1338 37.3 261 1352 35.9 272 1353 34.9 Alloy 14 228 1074 58.5 239 1077 54.1 230 1068 49.1 Alloy 15 206 991 60.9 208 1024 58.9 Alloy 16 199 1006 57.7 242 987 53.4 208 995 57.0 Alloy 17 222 844 72.6 197 867 64.9 213 869 66.5 Alloy 18 288 1415 32.6 300 1415 32.1 297 1421 29.6 Alloy 19 225 1032 58.5 213 1019 61.1 214 1017 58.4 Alloy 20 233 1111 57.3 227 1071 53.0 230 1091 49.4 Alloy 21 238 1073 50.6 228 1069 56.5 246 1110 52.0 Alloy 22 217 1157 47.0 236 1154 46.8 218 1154 47.7 Alloy 23 208 979 45.4 204 984 43.4 204 972 38.9 Alloy 28 277 811 86.7 279 802 86.0 277 799 82.0 Alloy 32 203 958 33.3 206 966 39.5 210 979 36.3 Alloy 34 216 1109 52.8 230 1144 55.9 231 1123 52.3 Alloy 35 230 1104 51.7 231 1087 59.0 220 1084 54.4

CASE EXAMPLES Case Example #1 Structural Development Pathway in Alloy 1

A laboratory slab with thickness of 50 mm was cast from Alloy 1 that was then laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 5 min as described in Main Body section of current application. Microstructure of the alloy was examined at each step of processing by SEM, TEM and x-ray analysis.

For SEM study, the cross section of the slab samples was ground on SiC abrasive papers with reduced grit size, and then polished progressively with diamond media paste down to 1 μm. The final polishing was done with 0.02 gm grit SiO₂ solution. Microstructures were examined by SEM using an EVO-MA10 scanning electron microscope manufactured by Carl Zeiss SMT Inc. To prepare TEM specimens, the samples were first cut by EDM, and then thinned by grinding with pads of reduced grit size every time. Further thinning to make foils of 60 to 70 μm thickness was done by polishing with 9 μm, 3 μm and 1 μm diamond suspension solution respectively. Discs of 3 mm in diameter were punched from the foils and the final polishing was completed with electropolishing using a twin-jet polisher. The chemical solution used was a 30% nitric acid mixed in methanol base. In case of insufficient thin area for TEM observation, the TEM specimens may be ion-milled using a Gatan Precision Ion Polishing System (PIPS). The ion-milling usually is done at 4.5 keV, and the inclination angle is reduced from 4° to 2° to open up the thin area. The TEM studies were done using a JEOL 2100 high-resolution microscope operated at 200 kV. X-ray diffraction was done using a PANalytical X'Pert MPD difftactometer with a Cu Kα x-ray tube and operated at 45 kV with a filament current of 40 mA. Scans were run with a step size of 0.01° and from 25° to 95° two-theta with silicon incorporated to adjust for instrument zero angle shift. The resulting scans were then subsequently analyzed using Rietveld analysis using Siroquant software.

Modal Structure was formed in the Alloy 1 slab with 50 mm thickness after solidification. The Modal Structure (Structure #1) is represented by a dendritic structure that is composed of several phases. In FIG. 6a , the backscattered SEM image shows the dendritic arms that are shown in dark contrast while the matrix phase is in bright contrast. Note that small casting pores are found as exhibited (black holes) in the SEM micrograph. TEM studies show that the matrix phase is primarily austenite (gamma-Fe) with stacking faults (FIG. 6b ). The presence of stacking faults indicates a face-centered-cubic structure (austenite). TEM also suggests that other phases could be formed in the Modal Structure. As shown in FIG. 6c , a dark phase is found that identified as a ferrite phase with body-centered cubic structure (alpha-Fe) according to selected electron diffraction pattern. X-ray diffraction analysis shows that the Modal Structure of the Alloy 1 contains austenite, ferrite, iron manganese compound and some martensite (FIG. 7). Generally, austenite is the dominant phase in the Alloy 1 Modal Structure, but other factors such as the cooling rate during commercial production may influence the formation of secondary phases such as martensite with varying volume fraction.

TABLE 11 X-ray Diffraction Data for Alloy 1 After Solidification (Modal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.583 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.876 Å Martensite Structure: Tetragonal Space group #: 139 (I4/mmm) LP: a = 2.898 Å c = 3.018 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.093 Å

Deformation of the Alloy 1 with the Modal Structure (Structure #1, FIG. 1A) at elevated temperature induces homogenization and refinement of Modal Structure. Hot rolling was applied in this case but other processes including but not limited to hot pressing, hot forging, hot extrusion can achieve the similar effect. During hot rolling, the dendrites in the Modal Structure are broken up and refined, leading initially to the Homogenized Modal Structure (Structure #1a, FIG. 1A) formation. The refinement during the hot rolling occurs through the Nanophase Refinement (Mechanism #1, FIG. 1A) along with dynamic recrystallization. The Homogenized Modal Structure can be progressively refined by applying the hot rolling repetitively, leading to the Nanomodal Structure (Structure #2, FIG. 1A) formation. FIG. 8a shows the backscattered SEM micrograph of Alloy 1 after being hot rolled from 50 mm to ˜1.7 mm at 1250° C. It can be seen that blocks of tens of microns in size are resulted from the dynamic recrystallization during the hot rolling, and the interior of the grains is relatively smooth indicating less amount of defects. TEM further reveals that sub-grains of less than several hundred nanometers in size are formed, as shown in FIG. 8b . X-ray diffraction analysis shows that the Nanomodal Structure of the Alloy 1 after hot rolling contains mainly austenite, with other phases such as ferrite and the iron manganese compound as shown in FIG. 9 and Table 12.

TABLE 12 X-ray Diffraction Data for Alloy 1 After Hot Rolling (Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.595 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.896 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.113 Å

Further deformation at ambient temperature (i.e., cold deformation) of the Alloy 1 with the Nanomodal Structure causes transformation into High Strength Nanomodal Structure (Structure #3, FIG. 1A) through the Dynamic Nanophase Strengthening (Mechanism #2, FIG. 1A). The cold deformation can be achieved by cold rolling and, tensile deformation, or other type of deformation such as punching, extrusion, stamping, etc. During the cold deformation, depending on alloy chemistries, a large portion of austenite in the Nanomodal Structure is transformed to ferrite with grain refinement. FIG. 10a shows the backscattered SEM micrograph of cold rolled Alloy 1. Compared to the smooth grains in the Nanomodal Structure after hot rolling, the cold deformed grains are rough indicating severe plastic deformation within the grains. Depending on alloy chemistry, deformation twins can be produced in some alloys especially by cold rolling, as displayed in FIG. 10a . FIG. 10b shows the TEM micrograph of the microstructure in cold rolled Alloy 1. It can be seen that in addition to dislocations generated by the deformation, refined grains due to phase transformation can also be found. The banded structure is related to the deformation twins caused by the cold rolling, corresponding to these in FIG. 10a . X-ray diffraction shows that the High Strength Nanomodal Structure of the Alloy 1 after cold rolling contains a significant amount of ferrite phase in addition to the retained austenite and the iron manganese compound as shown in FIG. 11 and Table 13.

TABLE 13 X-ray Diffraction Data for Alloy 1 after Cold Rolling (High Strength Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.588 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.871 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.102 Å

Recrystallization occurs upon heat treatment of the cold deformed Alloy 1 with High Strength Nanomodal Structure (Structure #3,FIG. 1A and 1B) that transforms into Recrystallized Modal Structure (Structure #4,FIG. 1B). The TEM images of the Alloy 1 after annealing are shown in FIG. 12. As it can be seen, equiaxed grains with sharp and straight boundaries are present in the structure and the grains are free of dislocations, which is characteristic feature of recrystallization. Depending on the annealing temperature, the size of recrystallized grains can range from 0.5 to 50 μm. In addition, as shown in electron diffraction shows that austenite is the dominant phase after recrystallization. Annealing twins are occasionally found in the grains, but stacking faults are most often seen. The formation of stacking faults shown in the TEM image is typical for face-centered-cubic crystal structure of austenite. Backscattered SEM micrographs in FIG. 13 show the equiaxed recrystallized grains with the size of less than 10 μm, consistent with TEM. The different contrast of grains (dark or bright) seen on SEM images suggests that the crystal orientation of the grains is random, since the contrast in this case is mainly originated from the grain orientation. As a result, any texture formed by the previous cold deformation is eliminated. X-ray diffraction shows that the Recrystallized Modal Structure of the Alloy 1 after annealing contains primarily austenite phase, with a small amount of ferrite and the iron manganese compound as shown in FIG. 14 and Table 14.

TABLE 14 X-ray Diffraction Data for Alloy 1 After Annealing (Recrystallized Modal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.597 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.884 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.103 Å

When the Alloy 1 with Recrystallized Modal Structure (Structure #4, FIG. 1B) is subjected to deformation at ambient temperature, Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B) is activated leading to formation of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B). In this case, deformation was a result of tensile testing and gage section of the tensile sample after testing was analyzed. FIG. 15 shows the bright-field TEM micrographs of the microstructure in the deformed Alloy 1. Compared to the matrix grains that were initially almost dislocation-free in the Recrystallized Modal Structure after annealing, the application of stress generates a high density of dislocations within the matrix grains. At the end of tensile deformation (with a tensile elongation greater than 50%), accumulation of large number of dislocations is observed in the matrix grains. As shown in FIG. 15a , in some areas (for example the area at the lower part of the FIG. 15a ), dislocations form a cell structure and the matrix remains austenitic. In other areas, where the dislocation density is sufficiently high, transformation is induced from austenite to ferrite (for example the upper and right part of the FIG. 15a ) that results in substantial structure refinement. FIG. 15b shows local “pocket” of the transformed refined microstructure and selected area electron diffraction pattern corresponds to ferrite. Structural transformation into Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) in the randomly distributed “pockets” is a characteristic feature of the steel alloys herein. FIG. 16 shows the backscattered SEM images of the Refined High Strength Nanomodal Structure. Compared to the Recrystallized Modal Structure, the boundaries of matrix grains become less apparent, and the matrix is obviously deformed. Although the details of deformed grains cannot be revealed by SEM, the change caused by the deformation is enormous compared to the Recrystallized Modal Structure that was demonstrated in TEM images. X-ray diffraction shows that the Refined High Strength Nanomodal Structure of the Alloy 1 after tensile deformation contains a significant amount of ferrite and austenite phases. Very broad peaks of ferrite phase (alpha-Fe) are seen in the XRD pattern, suggesting significant refinement of the phase. The iron manganese compound is also present. Additionally, a hexagonal phase with space group #186 (P6_(3mc)) was identified in the gage section of the tensile sample as shown in FIG. 17 and Table 15.

TABLE 15 X-ray Diffraction Data for Alloy 1 After Tensile Deformation (Refined High Strength Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.586 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.873 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.159 Å Hexagonal phase 1 Structure: Hexagonal Space group #: 186 (P6₃mc) LP: a = 3.013 Å, c = 6.183 Å

This Case Example demonstrates that alloys listed in Table 2 including Alloy 1 exhibit a structural development pathway with novel enabling mechanisms illustrated in FIGS. 1A and 1B leading to unique microstructures with nanoscale features.

Case Example #2 Structural Development Pathway in Alloy 2

Laboratory slab with thickness of 50 mm was cast from Alloy 2 that was then laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described in Main Body section of current application. Microstructure of the alloy was examined at each step of processing by SEM, TEM and x-ray analysis.

For SEM study, the cross section of the slab samples was ground on SiC abrasive papers with reduced grit size, and then polished progressively with diamond media paste down to 1 μm. The final polishing was done with 0.02 μm grit SiO₂ solution. Microstructures were examined by SEM using an EVO-MA10 scanning electron microscope manufactured by Carl Zeiss SMT Inc. To prepare TEM specimens, the samples were first cut with EDM, and then thinned by grinding with pads of reduced grit size every time. Further thinning to make foils to ˜60 μm thickness was done by polishing with 9 μm, 3 μm and 1 μm diamond suspension solution respectively. Discs of 3 mm in diameter were punched from the foils and the final polishing was fulfilled with electropolishing using a twin-jet polisher. The chemical solution used was a 30% nitric acid mixed in methanol base. In case of insufficient thin area for TEM observation, the TEM specimens may be ion-milled using a Gatan Precision Ion Polishing System (PIPS). The ion-milling usually is done at 4.5 keV, and the inclination angle is reduced from 4° to 2° to open up the thin area. The TEM studies were done using a JEOL 2100 high-resolution microscope operated at 200 kV. X-ray diffraction was done using a Panalytical X'Pert MPD diffractometer with a Cu Kα x-ray tube and operated at 45 kV with a filament current of 40 mA. Scans were run with a step size of 0.01° and from 25° to 95° two-theta with silicon incorporated to adjust for instrument zero angle shift. The resulting scans were then subsequently analyzed using Rietveld analysis using Siroquant software.

Modal Structure (Structure #1, FIG. 1A) is formed in Alloy 2 slab cast at 50 mm thick, which is characterized by dendritic structure. Due to the presence of a boride phase (M2B), the dendritic structure is more evident than in Alloy 1 where borides are absent. FIG. 18a shows the backscattered SEM of Modal Structure that exhibits a dendritic matrix (in bright contrast) with borides at the boundary (in dark contrast). TEM studies show that the matrix phase is composed of austenite (gamma-Fe) with stacking faults (FIG. 18b ). Similar to Alloy 1, the presence of stacking faults indicates the matrix phase is austenite. Also shown in TEM is the boride phase that appears dark in. FIG. 18b at the boundary of austenite matrix phase. X-ray diffraction analysis data in. FIG. 19 and Table 16 shows that the Modal Structure contains austenite, M₂B, ferrite, and iron manganese compound. Similar to Alloy 1, austenite is the dominant phase in the Alloy 2 Modal Structure, but other phases may be present depending on alloy chemistry.

TABLE 16 X-ray Diffraction Data for Alloy 2 After Solidification (Modal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.577 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.850 Å M₂B Structure: Tetragonal Space group #: 140 (I4/mcm) LP: a = 5.115 Å, c = 4.226 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.116 Å

Following the flowchart in FIG. 1A, deformation of the Alloy 2 with the Modal Structure (Structure #1, FIG. 1A) at elevated temperature induces homogenization and refinement of Modal Structure. Hot rolling was applied in this case but other processes including but not limited to hot pressing, hot forging, hot extrusion can achieve a similar effect. During the hot rolling, the dendrites in the Modal Structure are broken up and refined, leading initially to the Homogenized Modal Structure (Structure #1a, FIG. 1A) formation. The refinement during the hot rolling occurs through the Nanophase Refinement (Mechanism #1, FIG. 1A) along with dynamic recrystallization. The Homogenized Modal Structure can be progressively refined by applying the hot rolling repetitively, leading to the Nanomodal Structure (Structure #2, FIG. 1A) formation. FIG. 20a shows the backscattered SEM micrograph of hot rolled Alloy 2. Similar to Alloy 1, the dendritic Modal Structure is homogenized while the boride phase is randomly distributed in the matrix. TEM shows that the matrix phase is partially recrystallized as a result of dynamic recrystallization during hot rolling, as shown in FIG. 20b . The matrix grains are on the order of 500 nm, which is finer than in Alloy 1 due to the pinning effect of borides. X-ray diffraction analysis shows that the Nanomodal Structure of Alloy 2 after hot rolling contains mainly austenite phase and M₂B, with other phases such as ferrite and iron manganese compound as shown in FIG. 21 and Table 17.

TABLE 17 X-ray Diffraction Data for Alloy 2 After Hot Rolling (Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.598 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.853 Å M₂B Structure: Tetragonal Space group #: 140 (I4/mcm) LP: a = 5.123 Å, c = 4.182 Å Iron manganese Structure: Cubic compound Space group #: 225 (Fm3m) LP: a = 4.180 Å

Deformation of the Alloy 2 with the Nanomodal Structure but at ambient temperature (i.e., cold deformation) leads to formation of High Strength Nanomodal Structure (Structure #3, FIG. 1A) through the Dynamic Nanophase Strengthening (Mechanism #2, FIG. 1A). The cold deformation can be achieved by cold rolling, tensile deformation, or other type of deformation such as punching, extrusion, stamping, etc. Similarly in Alloy 2 during cold deformation, a great portion of austenite in the Nanomodal Structure is transformed to ferrite with grain refinement. FIG. 22a shows the backscattered SEM micrograph of the microstructure in the cold rolled Alloy 2. Deformation is concentrated in the matrix phase around the boride phase. FIG. 22b shows the TEM micrograph of the cold rolled Alloy 2. Refined grains can be found due to the phase transformation. Although deformation twins are less evident in SEM image, TEM shows that they are generated after the cold rolling, similar to Alloy 1. X-ray diffraction shows that the High Strength Nanomodal Structure of the Alloy 2 after cold rolling contains a significant amount of ferrite phase in addition to the M2B, retained austenite and a new hexagonal phase with space group #186 (P6_(3mc)) as shown in FIG. 23 and Table 18.

TABLE 18 X-ray Diffraction Data for Alloy 2 After Cold Rolling (High Strength Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.551 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.874 Å M₂B Structure: Tetragonal Space group #: 140 (I4/mcm) LP: a = 5.125 Å, c = 4.203 Å Hexagonal phase Structure: Hexagonal Space group #: 186 (P6₃mc) LP: a = 2.962 Å, c = 6.272 Å

Recrystallization occurs upon annealing of the cold deformed Alloy 2 with High Strength Nanomodal Structure (Structure #3, FIG. 1A and 1B) that transforms into Recrystallized Modal Structure (Structure #4, FIG. 1B). The recrystallized microstructure of the Alloy 2 after annealing is shown by TEM images in FIG. 24. As it can be seen, equiaxed grains with sharp and straight boundaries are present in the structure and the grains are free of dislocations, which is a characteristic feature of recrystallization. The size of recrystallized grains is generally less than 5 μm due to the pinning effect of boride phase, but larger grains are possible at higher annealing temperatures. Moreover, electron diffraction shows that austenite is the dominant phase after recrystallization and stacking faults are present in the austenite, as shown in FIG. 24b . The formation of stacking faults also indicates formation of face-centered-cubic austenite phase. Backscattered SEM micrographs in FIG. 25 show the equiaxed recrystallized grains with the size of less than 5 μm, with boride phase randomly distributed. The different contrast of grains (dark or bright) seen on SEM images suggests that the crystal orientation of the grains is random, since the contrast in this case is mainly originated from the grain orientation. As a result, any texture formed by the previous cold deformation is eliminated. X-ray diffraction shows that the Recrystallized Modal Structure of the Alloy 2 after annealing contains primarily austenite phase, with M₂B, a small amount of ferrite, and a hexagonal phase with space group #186 (P6_(3mc)) as shown in FIG. 26 and Table 19.

TABLE 19 X-ray Diffraction Data for Alloy 2 After Annealing (Recrystallized Modal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.597 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.878 Å M₂B Structure: Tetragonal Space group #: 140 (I4/mcm) LP: a = 5.153 Å, c = 4.170 Å Hexagonal phase Structure: Hexagonal Space group #: 186 (P6_(3mc)) LP: a = 2.965 Å, c = 6.270 Å

Deformation of Recrystallized Modal Structure (Structure #4, FIG. 1B) leads to formation of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) through Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B). In this case, deformation was a result of tensile testing and the gage section of the tensile sample after testing was analyzed. FIG. 27 shows the micrographs of microstructure in the deformed Alloy 2. Similar to Alloy 1, the initially dislocation-free matrix grains in the Recrystallized Modal Structure after annealing are filled with a high density of dislocations upon the application of stress, and the accumulation of dislocations in some grains activates the phase transformation from austenite to ferrite, leading to substantial refinement. As shown in FIG. 27a , refined grains of 100 to 300 nm in size are shown in a local “pocket” where transformation occurred from austenite to ferrite. Structural transformation into Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) in the “pockets” of matrix grains is a characteristic feature of the steel alloys herein. FIG. 27b shows the backscattered SEM images of the Refined High Strength Nanomodal Structure. Similarly, the boundaries of matrix grains become less apparent after the matrix is deformed. X-ray diffraction shows that a significant amount of austenite transformed to ferrite although the four phases remain as in the Recrystallized Modal Structure. The transformation resulted in formation of Refined High Strength Nanomodal Structure of the Alloy 2 after tensile deformation. Very broad peaks of ferrite phase (a-Fe) are seen in the XRI) pattern, suggesting significant refinement of the phase. As in Alloy 1, a new hexagonal phase with space group #186 (P6_(3mc)) was identified in the gage section of the tensile sample as shown in FIG. 28 and Table 20.

TABLE 20 X-ray Diffraction Data for Alloy 2 After Tensile Deformation (Refined High Strength Nanomodal Structure) Phases Identified Phase Details γ-Fe Structure: Cubic Space group #: 225 (Fm3m) LP: a = 3.597 Å α-Fe Structure: Cubic Space group #: 229 (Im3m) LP: a = 2.898 Å M₂B Structure: Tetragonal Space group #: 140 (14/mcm) LP: a = 5.149 Å, c = 4.181 Å Hexagonal phase Structure: Hexagonal Space group #: 186 (P6_(3mc)) LP: a = 2.961 Å, c = 6.271 Å

This Case Example demonstrates that alloys listed in Table 2 including Alloy 2 exhibit a structural development pathway with the mechanisms illustrated in FIGS. 1A and 1B leading to unique microstructures with nanoscale features.

Case Example #3 Tensile Properties at Each Step of Processing

Slabs with thickness of 50 mm were laboratory cast from the alloys listed in Table 21 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described in Main Body section of current application. Tensile properties were measured at each step of processing on an Instron 3369 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s. Strain data was collected using Instron's Advanced Video Extensometer.

Alloys were weighed out into charges ranging from 3,000 to 3,400 grams using commercially available ferroadditive powders with known chemistry and impurity content according to the atomic ratios in Table 2. Charges were loaded into zirconia coated silica crucibles which were placed into an Indutherm VTC800V vacuum tilt casting machine. The machine then evacuated the casting and melting chambers and backfilled with argon to atmospheric pressure several times prior to casting to prevent oxidation of the melt. The melt was heated with a 14 kHz RF induction coil until fully molten, approximately 5.25 to 6.5 minutes depending on the alloy composition and charge mass. After the last solids were observed to melt it was allowed to heat for an additional 30 to 45 seconds to provide superheat and ensure melt homogeneity. The casting machine then evacuated the melting and casting chambers and tilted the crucible and poured the melt into a 50 mm thick, 75 to 80 mm wide, and 125 mm deep channel in a water cooled copper die. The melt was allowed to cool under vacuum for 200 seconds before the chamber was filled with argon to atmospheric pressure. Tensile specimens were cut from as-cast slabs by wire EDM and tested in tension. Results of tensile testing are shown in Table 21. As it can be seen, ultimate tensile strength of the alloys herein in as-cast condition varies from 411 to 907 MPa. The tensile elongation varies from 3.7 to 24.4%. Yield strength is measured in a range from 144 to 514 MPa.

Prior to hot rolling, laboratory cast slabs were loaded into a Lucifer EHS3GT-B18 furnace to heat. The furnace set point varies between 1000° C. to 1250° C. depending on alloy melting point. The slabs were allowed to soak for 40 minutes prior to hot rolling to ensure they reach the target temperature. Between hot rolling passes the slabs are returned to the furnace for 4 minutes to allow the slabs to reheat. Pre-heated slabs were pushed out of the tunnel furnace into a Fenn Model 061 2 high rolling mill. The 50 mm casts are hot rolled for 5 to 8 passes through the mill before being allowed to air cool defined as first campaign of hot rolling. After this campaign the slab thickness was reduced between 80.4 to 87.4%. After cooling, the resultant sheet samples were sectioned to 190 mm in length. These sections were hot rolled for an additional 3 passes through the mill with reduction between 73.1 to 79.9% to a final thickness of between 2.1 and 1.6 mm. Detailed information on hot rolling conditions for each alloy herein is provided in Table 22. Tensile specimens were cut from hot rolled sheets by wire EDM and tested in tension. Results of tensile testing are shown in Table 22. After hot rolling, ultimate tensile strength of the alloys herein varies from 921 to 1413 MPa. The tensile elongation varies from 12.0 to 77.7%. Yield strength is measured in a range from 264 to 574 MPa. See, Structure 2 in FIG. 1A.

After hot rolling, resultant sheets were media blasted with aluminum oxide to remove the mill scale and were then cold roiled on a Fenn Model 061 2 high rolling mill. Cold rolling takes multiple passes to reduce the thickness of the sheet to targeted thickness, generally 1.2 mm. Hot rolled sheets were fed into the mill at steadily decreasing roll gaps until the minimum gap is reached. If the material has not yet hit the gauge target, additional passes at the minimum gap were used until the targeted thickness was reached. Cold rolling conditions with the number of passes for each alloy herein are listed in Table 23. Tensile specimens were cut from cold rolled sheets by wire EDM and tested in tension. Results of tensile testing are shown in Table 23. Cold rolling leads to significant strengthening with ultimate tensile strength in the range from 1356 to 1831 MPa. The tensile elongation of the alloys herein in cold rolled state varies from 1.6 to 32.1%. Yield strength is measured in a range from 793 to 1645 MPa. It is anticipated that higher ultimate tensile strength and yield strength can be achieved in alloys herein by larger cold rolling reduction (>40%) that in our case is limited by laboratory mill capability. With more rolling force, it is anticipated that ultimate tensile strength could be increased to at least 2000 MPa and yield strength to at least 1800 MPa.

Tensile specimens were cut from cold rolled sheet samples by wire EDM and annealed at 850° C. for 10 min in a Lucifer 7HT-K12 box furnace. Samples were removed from the furnace at the end of the cycle and allowed to cool to room temperature in air. Results of tensile testing are shown in Table 24. As it can be seen, recrystallization during annealing of the alloys herein results in property combinations with ultimate tensile strength in the range from 939 to 1424 MPa and tensile elongation from 15.8 to 77.0%. Yield strength is measured in a range from 420 to 574 MPa. FIG. 29 to FIG. 31 represent plotted data at each processing step for Alloy 1, Alloy 13, and Alloy 17, respectively.

TABLE 21 Tensile Properties of Alloys in As-Cast State Yield Strength Ultimate Tensile Tensile Elongation Alloy (MPa) Strength (MPa) (%) Alloy 1 289 527 10.4 288 548 9.3 260 494 8.4 Alloy 2 244 539 10.4 251 592 11.6 249 602 13.1 Alloy 13 144 459 4.6 156 411 4.5 163 471 5.7 Alloy 17 223 562 24.4 234 554 20.7 235 585 23.3 Alloy 24 396 765 8.3 362 662 5.7 404 704 7.0 Alloy 25 282 668 5.1 329 753 5.0 288 731 5.5 Alloy 25 471 788 4.1 514 907 6.0 483 815 3.7 Alloy 27 277 771 3.7 278 900 4.9 267 798 4.5 Alloy 34 152 572 11.1 168 519 11.6 187 545 12.9 Alloy 35 164 566 15.9 172 618 16.6 162 569 16.4

TABLE 22 Tensile Properties of Alloys in Hot Rolled State First Second Yield Ultimate Tensile Campaign Campaign Strength Tensile Elongation Alloy Condition Reduction Reduction (MPa) Strength (MPa) (%) Alloy Hot Rolled 80.5%, 75.1%, 273 1217 50.0 1 95.2% 6 Passes 3 Passes 264 1216 52.1 285 1238 52.7 Alloy Hot Rolled 87.4%, 73.1%, 480 1236 45.3 2 96.6% 7 Passes 3 Passes 454 1277 41.9 459 1219 48.2 Alloy Hot Rolled 81.1%, 79.8%, 287 1116 18.8 13 96.0% 6 Passes 3 Passes 274 921 15.3 293 1081 19.3 Alloy Hot Rolled 81.2%, 79.1%, 392 947 73.3 17 96.1% 6 Passes 3 Passes 363 949 74.8 383 944 77.7 Alloy Hot Rolled, 81.1%, 79.9%, 519 1176 21.4 24 96.2% 6 Passes 3 Passes 521 1088 18.2 508 1086 17.9 Alloy Hot Rolled 81.0%, 79.4%, 502 1105 12.4 25 96.1% 6 Passes 3 Passes 524 1100 12.3 574 1077 12.0 Alloy Hot Rolled, 80.4%, 78.9%, 508 1401 20.9 27 95.9% 6 Passes 3 Passes 534 1405 22.4 529 1413 19.7 Alloy Hot Rolled, 80.7%, 80.1%, 346 1188 56.5 34 96.2% 6 Passes 3 Passes 323 1248 58.7 303 1230 53.4 Alloy Hot Rolled, 80.8%, 79.9%, 327 1178 63.3 35 96.1% 6 Passes 3 Passes 317 1170 61.2 305 1215 59.6

TABLE 23 Tensile Properties of Alloys in Cold Rolled State Ultimate Yield Tensile Tensile Strength Strength Elongation Alloy Condition (MPa) (MPa) (%) Alloy 1 Cold Rolled 798 1492 28.5 20.3%, 793 1482 32.1 4 Passes Cold Rolled 1109 1712 21.4 39.6%, 1142 1726 23.0 29 Passes 1203 1729 21.2 Alloy 2 Cold Rolled 966 1613 13.4 28.5%, 998 1615 15.4 5 Passes 1053 1611 20.6 Cold Rolled 1122 1735 20.3 39.1%, 1270 1744 18.3 19 passes Alloy 13 Cold Rolled 1511 1824 9.5 36.0%, 1424 1803 7.7 24 Passes 1361 1763 5.1 Alloy 17 Cold Rolled 1020 1357 24.2 38.5%, 1007 1356 24.9 8 Passes 1071 1357 24.9 Alloy 24 Cold Rolled 1363 1584 1.9 38.2%, 1295 1601 2.5 23 Passes 1299 1599 3.0 Alloy 25 Cold Rolled 1619 1761 1.9 38.0%, 1634 1741 1.7 42 Passes 1540 1749 1.6 Alloy 27 Cold Rolled 1632 1802 2.7 39.4%, 1431 1804 4.1 40 Passes 1645 1831 4.1 Alloy 34 Cold Rolled 1099 1640 14.7 35.%, 840 1636 17.5 14 Passes 1021 1661 18.5 Alloy 35 Cold Rolled 996 1617 23.8 35.5%, 1012 1614 24.5 12 Passes 1020 1616 23.3

TABLE 24 Tensile Properties of Alloys in Annealed State Yield Strength Ultimate Tensile Tensile Elongation Alloy (MPa) Strength (MPa) (%) Alloy 1 436 1221 54.9 443 1217 56.0 431 1216 59.7 Alloy 2 438 1232 49.7 431 1228 49.8 431 1231 49.4 484 1278 48.3 485 1264 45.5 479 1261 48.7 Alloy 13 441 1424 41.7 440 1412 41.4 429 1417 42.7 Alloy 17 420 946 74.6 421 939 77.0 425 961 74.9 Alloy 24 554 1151 23.5 538 1142 24.3 562 1151 24.3 Alloy 25 500 1274 16.0 502 1271 15.8 483 1280 16.3 Alloy 27 538 1385 20.6 574 1397 20.9 544 1388 21.8 Alloy 27 467 1227 56.7 476 1232 52.7 462 1217 51.6 Alloy 27 439 1166 56.3 438 1166 59.0 440 1177 58.3

This Case Example demonstrates that due to the unique mechanisms and structural pathway shown in FIGS. 1A and 1B, the structures and resulting properties in steel alloys herein can vary widely leading to the development of 3^(rd) Generation AHSS.

Case Example #4 Cyclic Reversibility During Cold Rolling and Recrystallization

Slabs with thickness of 50 mm were laboratory cast from Alloy 1 and Alloy 2 according to the atomic ratios provided in Table 2 and hot rolled into sheets with final thickness of 2.31 mm for Alloy 1 sheet and 2.35 mm for Alloy 2 sheet. Casting and hot rolling procedures are described in Main Body section of current application. Resultant hot rolled sheet from each alloy was used for demonstration of cyclic structure/property reversibility through cold rolling/annealing cycles.

Hot rolled sheet from each alloy was subjected to three cycles of cold rolling and annealing. Sheet thicknesses before and after hot rolling and cold rolling reduction at each cycle are listed in Table 25. Annealing at 850° C. for 10 min was applied after each cold rolling. Tensile specimens were cut from the sheet in the initial hot rolled state and at each step of the cycling. Tensile properties were measured on an Instron 3369 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s Strain data was collected using Instron's Advanced Video Extensometer.

The results of tensile testing are plotted in FIG. 32 for Alloy 1 and Alloy 2 showing that cold rolling results in significant strengthening of both alloys at each cycle with average ultimate tensile strength of 1500 MPa in Alloy 1 and 1580 MPa in Alloy 2. Both cold rolled alloys show a loss in ductility as compared to the hot rolled state. However, annealing after cold rolling at each cycle results in tensile property recovery to the same level with high ductility.

Tensile properties for each tested sample are listed in Table 26 and Table 27 for Alloy 1 and Alloy 2, respectively. As it can be seen, Alloy 1 has ultimate tensile strength from 1216 to 1238 MPa in hot rolled state with ductility from 50.0 to 52.7% and yield strength from 264 to 285 MPa. In cold rolled state, the ultimate tensile strength was measured in the range from 1482 to 1517 MPa at each cycle. Ductility was found consistently in the range from 28.5 to 32.8% with significantly higher yield strength of 718 to 830 MPa as compared to that in hot rolled condition. Annealing at each cycle resulted in restoration of the ductility to the range from 47.7 to 59.7% with ultimate tensile strength from 1216 to 1270 MPa. Yield strength after cold rolling and annealing is lower than that after cold rolling and was measured in the range from 431 to 515 MPa that is however higher than that in initial hot rolled condition.

Similar results with property reversibility between cold rolled and annealed material through cycling were observed for Alloy 2 (FIG. 32b ). In initial hot rolled state, Alloy 2 has ultimate tensile strength from 1219 to 1277 MPa with ductility from 41.9 to 48.2% and yield strength from 454 to 480 MPa. Cold rolling at each cycle results in the material strengthening to the ultimate tensile strength from 1553 to 1598 MPa with ductility reduction to the range from 20.3 to 24.1%. Yield strength was measured from 912 to 1126 MPa. After annealing at each cycle, Alloy 2 has ultimate tensile strength from 1231 to 1281 MPa with ductility from 46.9 to 53.5%. Yield strength in Alloy 2 after cold rolling and annealing at each cycle is similar to that in hot rolled condition and varies from 454 to 521 MPa.

TABLE 25 Sample Thickness and Cycle Reduction at Cold Rolling Steps Rolling Initial Thickness Final Thickness Cycle Reduction Alloy Cycle (mm) (mm) (%) Alloy 1 1 2.35 1.74 26.0 2 1.74 1.32 24.1 3 1.32 1.02 22.7 Alloy 2 1 2.31 1.85 19.9 2 1.85 1.51 18.4 3 1.51 1.22 19.2

TABLE 26 Tensile Properties of Alloy 1 Through Cold Rolling/Annealing Cycles 1st Cycle 2nd Cycle 3rd Cycle Cold Cold Cold Property Hot Rolled Rolled Annealed Rolled Annealed Rolled Annealed Ultimate 1217 1492 1221 1497 1239 1517 1270 Tensile 1216 1482 1217 1507 1269 1507 1262 Strength 1238 * 1216 1503 1260 1507 1253 (MPa) Yield 273 798 436 775 487 820 508 Strength 264 793 443 718 466 796 501 (MPa) 285 * 431 830 488 809 515 Tensile 50.0 28.5 54.9 32.8 57.5 32.1 50.5 Elongation 52.1 32.1 56.0 29.4 52.5 30.2 47.7 (%) 52.7 * 59.7 30.9 55.8 30.5 55.5 * Specimens slipped in the grips/data is not available

TABLE 27 Tensile Properties of Alloy 2 Through Cold Rolling/Annealing Cycles 1st Cycle 2nd Cycle 3rd Cycle Cold Cold Cold Property Hot Rolled Rolled Annealed Rolled Annealed Rolled Annealed Ultimate 1236 1579 1250 1553 1243 1596 1231 Tensile 1277 * 1270 1568 1255 1589 1281 Strength 1219 * 1240 1566 1242 1598 1269 (MPa) Yield 480 1126 466 983 481 1006 475 Strength 454 * 468 969 521 978 507 (MPa) 459 * 454 912 497 1011 518 Tensile 45.3 20.3 53.0 24.1 51.1 22.3 46.9 Elongation 41.9 * 51.2 23.1 52.3 23.2 53.5 (%) 48.2 * 51.1 21.6 49.9 21.0 47.9 * Specimens slipped in the grips/data is not available

This Case Example demonstrates that the High Strength Nanomodal Structure (Structure #3, FIG. 1A) that forms in the alloys listed in Table 2 after cold rolling can be recrystallized by applying an anneal to produce a Recrystallized Modal Structure (Structure #4, FIG. 1B). This structure can be further deformed through cold rolling or other cold deformation approaches to undergo Nanophase Refinement and Strengthening (Mechanism #4, FIG. 1B) leading to formation of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B). The Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) can in turn be recrystallized and the process can be started over with full structure/property reversibility through multiple cycles. The ability for the mechanisms to be reversible enables the production of finer gauges which are important for weight reduction when using AHSS as well as property recovery after any damage caused by deformation.

Case Example #5 Bending Ability

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 28 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described in Main Body section of current application. Resultant sheet from each alloy with final thickness of ˜1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to evaluate bending response of alloys herein.

Bend tests were performed using an Instron 5984 tensile test platform with an Instron W-6810 guided bend test fixture according to specifications outlined in the ISO 7438 International Standard Metallic materials—Bend test (International Organization for Standardization, 2005). Test specimens were cut by wire EDM to a dimension of 20 mm×55 mm×sheet thickness. No special edge preparation was done to the samples. Bend tests were performed using an Instron 5984 tensile test platform with an Instron W-6810 guided bend test fixture. Bend tests were performed according to specifications outlined in the ISO 7438 International Standard Metallic materials—Bend test (International Organization for Standardization, 2005).

The test was performed by placing the test specimen on the fixture supports and pushing with a former as shown in FIG. 33.

The distance between supports, l, was fixed according to ISO 7438 during the test at:

$\begin{matrix} {l = {\left( {D + {3a}} \right) \pm \frac{a}{2}}} & {{Equation}\mspace{14mu} 1} \end{matrix}$

Prior to bending, the specimens were lubricated on both sides with 3 in 1 oil to reduce friction with the test fixture. This test was performed with a 1 mm diameter former. The former was pushed downward in the middle of the supports to different angles up to 180° or until a crack appeared. The bending force was applied slowly to permit free plastic flow of the material. The displacement rate was calculated based on the span gap of each test in order to have a constant angular rate and applied accordingly.

Absence of cracks visible without the use of magnifying aids was considered evidence that the test piece withstood the bend test. If a crack was detected, the bend angle was measured manually with a digital protractor at the bottom of the bend. The test specimen was then removed from the fixture and examined for cracking on the outside of the bend radius. The onset of cracking could not be conclusively determined from the force-displacement curves and was instead easily determined by direct observation with illumination from a flashlight.

Results of the bending response of the alloys herein are listed in Table 28 including initial sheet thickness, former radius to sheet thickness ratio WO and maximum bend angle before cracking. All alloys listed in the Table 28 did not show cracks at 90° bend angle. The majority of the alloys herein have capability to be bent at 180° angle without cracking. Example of the samples from Alloy 1 after bend testing to 180° is shown in FIG. 34.

TABLE 7 Bend Test Results for Selected Alloys Former Diameter Thickness Maximum Bend Alloy (mm) (mm) r/t Angle (°) Alloy 1 0.95 1.185 0.401 180 1.200 0.396 180 1.213 0.392 180 1.223 0.388 180 1.181 0.402 180 1.187 0.400 180 1.189 0.399 180 1.206 0.394 180 Alloy 2 0.95 1.225 0.388 180 1.230 0.386 180 1.215 0.391 180 1.215 0.391 180 1.215 0.391 180 1.224 0.388 180 1.208 0.393 180 1.208 0.393 180 Alloy 3 0.95 1.212 0.392 180 1.186 0.401 180 1.201 0.396 180 Alloy 4 0.95 1.227 0.387 180 1.185 0.401 180 1.187 0.400 180 Alloy 5 0.95 1.199 0.396 110 1.196 0.397 90 Alloy 6 0.95 1.259 0.377 160 1.202 0.395 165 1.206 0.394 142 Ahoy 7 0.95 1.237 0.384 104 1.236 0.384 90 Alloy 9 0.95 1.278 0.372 180 1.197 0.397 180 1.191 0.399 180 Alloy 10 0.95 1.226 0.387 180 1.208 0.393 100 1.208 0.393 180 1.205 0.394 180 Alloy 11 0.95 1.240 0.383 180 1.214 0.391 180 1.205 0.394 180 Alloy 12 0.95 1.244 0.382 180 1.215 0.391 180 1.205 0.394 180 Alloy 13 0.95 1.222 0.389 180 1.191 0.399 180 1.188 0.400 180 Alloy 14 0.95 1.239 0.383 180 1.220 0.389 180 1.214 0.391 180 Alloy 15 0.95 1.247 0.381 180 1.224 0.388 180 1.224 0.388 180 Alloy 16 0.95 1.244 0.382 180 1.224 0.388 180 1.199 0.396 180 Alloy 17 0.95 1.233 0.385 180 1.213 0.392 180 1.203 0.395 180 Alloy 18 0.95 1.222 0.389 160 1.218 0.390 135 Alloy 19 0.95 1.266 0.375 180 1.243 0.382 180 1.242 0.382 180 Alloy 20 0.95 1.242 0.382 180 1.222 0.389 180 1.220 0.389 180 Alloy 21 0.95 1.255 0.378 180 1.228 0.387 180 1.229 0.386 180 Alloy 22 0.95 1.240 0.383 180 1.190 0.399 180 1.190 0.399 180 Alloy 23 0.95 1.190 0.399 180 1.199 0.396 180 1.193 0.398 180 Alloy 28 0.95 1.222 0.389 180 1.206 0.394 180 1.204 0.395 180 Alloy 29 0.95 1.219 0.390 180 1.217 0.390 180 1.206 0.394 180 Alloy 30 0.95 1.215 0.391 180 1.212 0.392 175 1.200 0.396 180 Alloy 31 0.95 1.211 0.392 150 1.209 0.393 131 Alloy 32 0.95 1.222 0.389 180 1.221 0.389 180 1.210 0.393 180

In order to be made into complex parts for automobile and other uses, an AHSS needs to exhibit both bulk sheet formability and edge sheet formability. This Case Example demonstrates good bulk sheet formability of the alloys in Table 2 through bend testing.

Case Example #6 Punched Edge vs EDM Cut Tensile Properties

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 2according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) were used to evaluate the effect of edge damage on alloy properties by cutting tensile specimens by wire electrical discharge machining (wire-EDM) (which represents the control situation or relative lack of shearing and formation of an edge without a compromise in mechanical properties) and by punching (to identify a mechanical property loss due to shearing). It should be appreciated that shearing (imposition of a stress coplanar with a material cross-section) may occur herein by a number of processing options, such as piercing, perforating, cutting or cropping (cutting off of an end of a given metal part).

Tensile specimens in the ASTM E8 geometry were prepared using both wire EDM cutting and punching. Tensile properties were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s. Strain data was collected using Instron's Advanced Video Extensometer. Tensile data is shown in Table 29 and illustrated in FIG. 35a for selected alloys. Decrease in properties is observed for all alloys tested but the level of this decrease varies significantly depending on alloy chemistry. Table 30 summarizes a comparison of ductility in punched samples as compared to that in the wire EDM cut samples. In FIG. 35b corresponding tensile curves are shown for the selected alloy demonstrating mechanical behavior as a function of austenite stability. For selected alloys herein, austenite stability is highest in Alloy 12 that shows high ductility and lowest in Alloy 13 that shows high strength. Correspondingly, Alloy 12 demonstrated lowest loss in ductility in punched specimens vs EDM cut (29.7% vs 60.5%, Table 30) while Alloy 13 demonstrated highest loss in ductility in punched specimens vs EDM cut (5.2% vs 39.1%, Table 30). High edge damage occurs in punched specimens from alloy with lower austenite stability.

TABLE 8 Tensile Properties of Punched vs EDM Cut Specimens from Selected Alloys Cutting Yield Strength Ultimate Tensile Tensile Alloy Method (MPa) Strength (MPa) Elongation (%) Alloy 1 EDM Cut 392 1310 46.7 397 1318 45.1 400 1304 49.7 Punched 431 699 9.3 430 680 8.1 422 656 6.9 Alloy 2 EDM Cut 434 1213 46.4 452 1207 46.8 444 1199 49.1 Punched 491 823 14.4 518 792 11.3 508 796 11.9 Alloy 9 EDM Cut 468 1166 56.1 480 1177 52.4 475 1169 56.9 Punched 508 1018 29.2 507 1007 28.6 490 945 23.3 Alloy 11 EDM Cut 474 1115 64.4 464 1165 62.5 495 1127 62.7 Punched 503 924 24.6 508 964 28.0 490 921 25.7 Alloy 12 EDM Cut 481 1094 54.4 479 1128 64.7 495 1126 62.4 Punched 521 954 27.1 468 978 30.7 506 975 31.2 Alloy 13 EDM Cut 454 1444 39.5 450 1455 38.7 Punched 486 620 5.0 469 599 6.3 483 616 4.5 Alloy 14 EDM Cut 484 1170 58.7 489 1182 61.2 468 1188 59.0 Punched 536 846 17.0 480 816 18.4 563 870 17.5 Alloy 18 EDM Cut 445 1505 37.8 422 1494 37.5 Punched 478 579 2.4 469 561 2.6 463 582 2.9 Alloy 21 EDM Cut 464 1210 57.6 499 1244 49.0 516 1220 54.5 Punched 527 801 11.3 511 806 12.6 545 860 15.2 Alloy 24 EDM Cut 440 1166 31.0 443 1167 32.0 455 1176 31.0 Punched 496 696 5.0 463 688 5.0 440 684 4.0 Alloy 25 EDM Cut 474 1183 15.8 470 1204 17.0 485 1223 17.4 Punched 503 589 2.1 517 579 0.8 497 583 2.1 Alloy 26 EDM Cut 735 1133 20.8 742 1109 19.0 Punched 722 898 3.4 747 894 2.9 764 894 3.1 Alloy 27 EDM Cut 537 1329 19.3 513 1323 21.4 480 1341 20.8 Punched 563 624 4.3 568 614 3.3 539 637 4.3 Alloy 34 EDM Cut 460 1209 54.7 441 1199 54.1 475 1216 52.9 Punched 489 828 15.4 486 811 14.6 499 813 14.8 Alloy 35 EDM Cut 431 1196 50.6 437 1186 52.0 420 1172 54.7 Punched 471 826 19.9 452 828 19.7 482 854 19.7

TABLE 9 Tensile Elongation in Specimens with Different Cutting Methods Loss In Tensile Elongation Average Tensile Elongation (%) (E2/E1) Alloy EDM Cut (E1) Punched (E2) Min Max Alloy 1 47.2 8.1 0.14 0.21 Alloy 2 47.4 12.5 0.23 0.31 Alloy 9 55.1 27.0 0.41 0.56 Alloy 11 63.2 26.1 0.38 0.45 Alloy 12 60.5 29.7 0.42 0.57 Alloy 13 39.1 5.2 0.11 0.16 Alloy 14 59.7 17.7 0.28 0.31 Alloy 18 37.6 2.6 0.06 0.08 Alloy 21 53.7 13.0 0.20 0.31 Alloy 24 31.3 4.7 0.13 0.16 Alloy 25 16.7 1.7 0.05 0.13 Alloy 26 31.3 4.7 0.14 0.18 Alloy 27 20.5 4.0 0.15 0.22 Alloy 34 53.9 14.9 0.27 0.29 Alloy 35 52.4 19.8 0.36 0.39

As can be seen from Table 30, EDM cutting is considered to be representative of the optimal mechanical properties of the identified alloys, without a sheared edge, and which were processed to the point of assuming Structure #4 (Recrystallized Modal Structure). Accordingly, samples having a sheared edge due to punching indicate a significant drop in ductility as reflected by tensile elongation measurements of the punched samples having the ASTM E8 geometry. For Alloy 1, tensile elongation is initially 47.2% and then drops to 8.1%, a drop itself of 82.8%%. The drop in ductility from the punched to the EDM cut (E2/E1) varies from 0.57 to 0.05.

The edge status after punching and EDM cutting was analyzed by SEM using an EVO-MA10 scanning electron microscope manufactured by Carl Zeiss SMT Inc. The typical appearance of the specimen edge after EDM cutting is shown for Alloy 1 in FIG. 36a . The EDM cutting method minimizes the damage of a cut edge allowing the tensile properties of the material to be measured without any deleterious edge effects. In wire-EDM cutting, material is removed from the edge by a series of rapidly recurring current discharges/sparks and by this route an edge is formed without substantial deformation or edge damage. The appearance of the sheared edge after punching is shown in FIG. 36b . A significant damage of the edge occurs in a fracture zone that undergoes severe deformation during punching leading to structural transformation in the shear affected zone into a Refined High Strength Nanomodal Structure (FIG. 37b ) with limited ductility while Recrystallized Modal Structure was observed near EDM cut edge (FIG. 37a ).

This Case Example demonstrates that in a case of wire-EDM cutting tensile properties are measured at relative higher level as compared to that after punching. In contrast to EDM cutting, punching of the tensile specimens creates a significant edge damage which results in tensile property decrease. Relative excessive plastic deformation of the sheet alloys herein during punching leads to structural transformation to a Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) with reduced ductility leading to premature cracking at the edge and relatively lower properties (e.g. reduction in elongation and tensile strength). The magnitude of this drop in tensile properties has also been observed to depend on the alloy chemistry in correlation with austenite stability.

Case Example #7 Punched Edge vs EDM Cut Tensile Properties and Recovery

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 31 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to demonstrate edge damage recovery by annealing of punched tensile specimens. In the broad context of the present invention, annealing may be achieved by various methods, including but not limited to furnace heat treatment, induction heat treatment and/or laser heat treatment.

Tensile specimens in the ASTM E8 geometry were prepared using both wire EDM cutting and punching. Part of punched tensile specimens was then put through a recovery anneal of 850° C. for 10 minutes, followed by an air cool, to confirm the ability to recover properties lost by punching and shearing damage. Tensile properties were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 min/s. Strain data was collected using Instron's Advanced Video Extensometer. Tensile testing results are provided in Table 31 and illustrated in FIG. 38 for selected alloys showing a substantial mechanical property recovery in punched samples after annealing.

For example, in the case of Alloy 1 indicated, when EDM cut into a tensile testing sample, a tensile elongation average value is about 47.2%. As noted above, when punched and therefore containing a sheared edge, the tensile testing of the sample with such edge indicated a significant drop in such elongation values, i.e. an average value of only about 8.1% due to Mechanism #4 and formation of Refined High Strength Nanomodal Structure (Structure 45 FIG. 1B), which while present largely at the edge section where shearing occurred, is nonetheless reflected in the bulk property measurements in tensile testing. However, upon annealing, which is representative of Mechanism #3 in FIG. 1B and conversion to Structure #4 (Recrystallized Modal Structure, FIG. 1B), the tensile elongation properties are restored. In the case of Alloy 1, the tensile elongation are brought back to an average value of about 46.2%. Example tensile stress-strain curves for punched specimens from Alloy 1 with and without annealing are shown in FIG. 39. In Table 32, a summary of the average tensile properties and the average lost and gained in tensile elongation is provided. Note that the individual losses and gains are a larger spread than the average losses. Accordingly, in the context of the present disclosure, the alloys herein, having an initial value of tensile elongation (Eu) when sheared, may indicate a drop in elongation properties to a value of E₂, wherein E₂=(0.0.57 to 0.05)(E₁). Then, upon application of Mechanism #3, which is preferably accomplished by heating/annealing at a temperature range of 450° C. up to the T_(m) depending on alloy chemistry, the value of E₂ is recovered to an elongation value E₃=(0.48 to 1.21)(E₁).

TABLE 10 Tensile Properties of Punched and Annealed Specimens from Selected Alloys Ultimate Yield Tensile Tensile Cutting Strength Strength Elongation Alloy Method (MPa) (MPa) (%) Alloy 1 EDM Cut 392 1310 46.7 397 1318 45.1 400 1304 49.7 Punched 431 699 9.3 430 680 8.1 422 656 6.9 Punched & 364 1305 43.6 Annealed 364 1315 47.6 370 1305 47.3 Alloy 2 EDM Cut 434 1213 46.4 452 1207 46.8 444 1199 49.1 Punched 491 823 14.4 518 792 11.3 508 796 11.9 Punched & 432 1205 50.4 Annealed 426 1191 50.7 438 1188 49.3 Alloy 9 EDM Cut 468 1166 56.1 480 1177 52.4 475 1169 56.9 Punched 508 1018 29.2 507 1007 28.6 490 945 23.3 Punched & 411 1166 59.0 Annealed 409 1174 52.7 418 1181 55.6 Alloy 11 EDM Cut 474 1115 64.4 464 1165 62.5 495 1127 62.7 Punched 503 924 24.6 508 964 28.0 490 921 25.7 Punched & 425 1128 64.5 Annealed 429 1117 57.1 423 1140 54.3 Alloy 12 EDM Cut 481 1094 54.4 479 1128 64.7 495 1126 62.4 Punched 521 954 27.1 468 978 30.7 506 975 31.2 Punched & 419 1086 65.7 Annealed 423 1085 63.0 415 1100 53.8 Alloy 13 EDM Cut 454 1444 39.5 450 1455 38.7 Punched 486 620 5.0 469 599 6.3 483 616 4.5 Punched & 397 1432 41.4 Annealed 397 1437 37.4 404 1439 40.3 Alloy 14 EDM Cut 484 1170 58.7 489 1182 61.2 468 1188 59.0 Punched 536 846 17.0 480 816 18.4 563 870 17.5 Punched & 423 1163 58.3 Annealed 412 1168 55.9 415 1177 51.5 Alloy 18 EDM Cut 445 1505 37.8 422 1494 37.5 Punched 478 579 2.4 469 561 2.6 463 582 2.9 Punched & 398 1506 36.3 Annealed 400 1502 40.3 392 1518 35.4 Alloy 21 EDM Cut 464 1210 57.6 499 1244 49.0 516 1220 54.5 Punched 527 801 11.3 511 806 12.6 545 860 15.2 Punched & 409 1195 47.7 Annealed 418 1214 53.8 403 1194 51.8 Alloy 24 EDM Cut 440 1166 31.0 443 1167 32.0 455 1176 31.0 Punched 496 696 5.0 463 688 5.0 440 684 4.0 Punched & 559 1100 22.3 Annealed 581 1113 22.0 561 1100 22.3 Alloy 25 EDM Cut 474 1183 15.8 470 1204 17.0 485 1223 17.4 Punched 503 589 2.1 517 579 0.8 497 583 2.1 Punched & 457 1143 15.4 Annealed 477 1159 14.6 423 1178 16.3 Alloy 26 EDM Cut 735 1133 20.8 742 1109 19.0 Punched 722 898 3.4 747 894 2.9 764 894 3.1 Punched & 715 1112 18.8 Annealed 713 1098 17.8 709 931 10.0 Alloy 27 EDM Cut 537 1329 19.3 513 1323 21.4 480 1341 20.8 Punched 563 624 4.3 568 614 3.3 539 637 4.3 Punched & 505 1324 19.7 Annealed 514 1325 20.0 539 1325 19.4 Alloy 29 EDM Cut 460 1209 54.7 441 1199 54.1 475 1216 52.9 Punched 489 828 15.4 486 811 14.6 499 813 14.8 Punched & 410 1204 53.9 Annealed 410 1220 53.2 408 1214 52.3 Alloy 32 EDM Cut 431 1196 50.6 437 1186 52.0 420 1172 54.7 Punched 471 826 19.9 452 828 19.7 482 854 19.7 Punched & 406 1169 58.1 Annealed 403 1170 51.4 405 1176 57.7

TABLE 32 Summary of Tensile Properties; Loss (E2/E1) and Gain (E3/E1) Loss In Tensile Elongation Gain in Tensile Elongation (E2/E1) (E3/E1) Alloy Min Max Min Max Alloy 1 0.14 0.21 0.88 1.06 Alloy 2 0.23 0.31 1.00 1.09 Alloy 9 0.41 0.56 0.93 1.13 Alloy 11 0.38 0.45 0.84 1.03 Alloy 12 0.42 0.57 0.83 1.21 Alloy 13 0.11 0.16 0.95 1.07 Alloy 14 0.28 0.31 0.84 0.99 Alloy 18 0.06 0.08 0.94 1.07 Alloy 21 0.20 0.31 0.83 1.10 Alloy 24 0.13 0.16 0.69 0.72 Alloy 25 0.05 0.13 0.89 1.03 Alloy 26 0.14 0.18 0.48 0.99 Alloy 27 0.15 0.22 0.91 1.04 Alloy 29 0.27 0.29 0.97 1.02 Alloy 32 0.36 0.39 0.94 1.15

Punching of tensile specimens results in edge damage and lowering the tensile properties of the material. Plastic deformation of the sheet alloys herein during punching leads to structural transformation to a Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) with reduced ductility leading to premature cracking at the edge and relatively lower properties (e.g. reduction in elongation and tensile strength). This Case Example demonstrates that due to the unique structural reversibility, the edge damage in the alloys listed in Table 2 is substantially recoverable by annealing leading back to Recrystallized Modal Structure (Structure #4, FIG. 1B) formation with full or partial property restoration that depends on alloy chemistry and processing. For example, as exemplified by Alloy 1, punching and shearing and creating a sheared edge is observed to reduce tensile strength from an average of about 1310 MPa (an EDM cut sample without a sheared/damaged edge) to an average value of 678 MPa, a drop of between 45 to 50%. Upon annealing, tensile strength recovers to an average value of about 1308 MPa, which is in the range of greater than or equal to 95% of the original value of 1310 MPa. Similarly, tensile elongation is initially at an average of about 47.1%, dropping to an average value of 8.1%, a decrease of up to about 80 to 85%, and upon annealing and undergoing what is shown in FIG. 1B as Mechanism #3, tensile elongation recovers to an average value of 46.1%, a recovery of greater than or equal to 90% of the value of the elongation value of 47.1%.

Case Example #8 Temperature Effect on Recovery and Recrystallization

Slabs with thickness of 50 mm were laboratory cast from Alloy 1 and laboratory processed by hot rolling down to thickness of 2 mm and cold rolling with reduction of approximately 40%. Tensile specimens in the ASTM E8 geometry were prepared by wire EDM cut from cold rolled sheet. Part of tensile specimens was annealed for 10 minutes at different temperatures in a range from 450 to 850° C., followed by an air cool. Tensile properties were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s. Strain data was collected using Instron's Advanced Video Extensometer. Tensile testing results are shown in FIG. 40 demonstrating a transition in deformation behavior depending on annealing temperature. During the process of cold rolling, the Dynamic Nanophase Strengthening (Mechanism #2, FIG. 1A) or the Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B) occurs which involves, once the yield strength is exceeded with increasing strain, the continuous transformation of austenite to ferrite plus one or more types of nanoscale hexagonal phases. Concurrent with this transformation, deformation by dislocation mechanisms also occurs in the matrix grains prior to and after transformation. The result is the change in the microstructure from the Nanomodal Structure (Structure #2, FIG. 1A) to the High Strength Nanomodal Structure (Structure #3, FIG. 1A) or from the Recrystallized Modal Structure (Structure #4, FIG. 1B) to the Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B). The structure and property changes occurring during cold deformation can be reversed at various degrees by annealing depending on annealing parameters as seen in the tensile curves of FIG. 40A. In FIG. 40B, the corresponding yield strength from the tensile curves are provided as a function of the heat treatment temperature. The yield strength after cold rolling with no anneal is measured at 1141 MPa. As shown, depending on how the material is annealed which may include partial and full recovery and partial and full recrystallization the yield strength can be varied widely from 1372 MPa at the 500° C. anneal down to 458 MPa at the 850° C. anneal.

To show the microstructural recovery in accordance to the tensile property upon annealing, TEM studies were conducted on selected samples that were annealed at different temperatures. For comparison, cold rolled sheet was included as a baseline herein. Laboratory cast Alloy 1 slab of 50 mm thick was used, and the slab was hot rolled at 1250° C. by two-step of 80.8% and 78.3% to approx. 2 mm thick, then cold rolled by 37% to sheet of 1.2 mm thick. The cold rolled sheet was annealed at 450° C., 600° C., 650° C. and 700° C. respectively for 10 minutes. FIG. 41 shows the microstructure of as-cold rolled Alloy 1 sample. It can be seen that typical High Strength Nanomodal Structure is formed after cold rolling, in which high density of dislocations are generated along with the presence of strong texture. Annealing at 450° C. for 10 min does not lead to recrystallization and formation of the High Strength Nanomodal Structure, as the microstructure remains similar to that of the cold rolled structure and the rolling texture remains unchanged (FIG. 42). When the cold rolled sample is annealed at 600° C. for 10 min, TEM analysis shows very small isolated grains, a sign of the beginning of recrystallization. As shown in FIG. 43, isolated grains of 100 nm or so are produced after the annealing, while areas of deformed structure with dislocation networks are also present. Annealing at 650° C. for 10 min shows larger recrystallized grains suggesting the progress of recrystallization. Although the fraction of deformed area is reduced, the deformed structure continues to be seen, as shown in FIG. 44. Annealing at 700° C. 10 min shows larger and cleaner recrystallized grains, as displayed by FIG. 45. Selected electron diffraction shows that these recrystallized grains are of the austenite phase. The area of deformed structure is smaller compared to the samples annealed at lower temperature. Survey over the entire sample suggests that approx. 10% to 20% area is occupied by the deformed structure. The progress of recrystallization revealed by TEM in the samples annealed at lower temperature to higher temperature corresponds excellently to the change of tensile properties shown in FIG. 40. These low temperature annealed samples (such as below 600° C.) maintain predominantly the High Strength Nanomodal Structure, leading to the reduced ductility. The recrystallized sample (such as at 700° C.) recovers majority of the elongation, compared to the fully recrystallized sample at 850° C. The annealing in between these temperatures partially recovers the ductility.

One reason behind the difference in recovery and transition in deformation behavior is illustrated by the model TTT diagram in FIG. 46. As described previously, the very fine/nanoscale grains of ferrite formed during cold working recrystallize into austenite during annealing and some fraction of the nanoprecipitates re-dissolve. Concurrently, the effect of the strain hardening is eliminated with dislocation networks and tangles, twin boundaries, and small angle boundaries being annihilated by various known mechanisms. As shown by the heating curve A of the model temperature, time transformation (TTT) diagram in FIG. 46, at low temperatures (particularly below 650° C. for Alloy 1), only recovery may occur without recrystallization (i.e. recovery being a reference to a reduction in dislocation density).

In other words, in the broad context of the present invention, the effect of shearing and formation of a sheared edge, and its associated negative influence on mechanical properties, can be at least partially recovered at temperatures of 450° C. up to 650° C. as shown in FIG. 46. In addition, at 650° C. and up to below Tm of the alloy, recrystallization can occur, which also contributes to restoring mechanical strength lost due to the formation of a sheared edge.

Accordingly, this Case Example demonstrates that upon deformation during cold rolling, concurrent processes occur involving dynamic strain hardening and phase transformation through unique Mechanisms #2 or #3 (FIG. 1A) along with dislocation based mechanisms. Upon heating, the microstructure can be reversed into a Recrystallized Modal Structure (Structure #4, FIG. 1B). However, at low temperatures, this reversing process may not occur when only dislocation recovery takes place. Thus, due to the unique mechanisms of the alloys in Table 2, various external heat treatments can be used to heal the edge damage from punching/stamping.

Case Example #9 Temperature Effect of Punched Edge Recovery

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 33 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described in Main Body section of current application. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to demonstrate punched edge damage recovery after annealing as a function of temperature.

Tensile specimens in the ASTM E8 geometry were prepared by punching. A part of punched tensile specimens from selected alloys was then put through a recovery anneal for 10 minutes at different temperatures in a range from 450 to 850° C., followed by an air cool. Tensile properties were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 mm/s. Strain data was collected using Instron's Advanced Video Extensometer.

Tensile testing results are shown in Table 32 and in FIG. 47. As it can be seen, full or nearly full property recovery achieved after annealing at temperatures at 650° C. and higher, suggesting that the structure is fully or near fully recrystallized (i.e. change in structure from Structure #5 to Structure #1 in FIG. 1B) in the damaged edges after punching. For example, the level of recrystallization at the damaged edge is contemplated to be at a level of greater than or equal to 90% when annealing temperatures are in the range of 650° C. up to T_(m). Lower annealing temperature (e.g. temperatures below 650° C. does not result in full recrystallization and leads to partial recovery (i.e. decrease in dislocation density) as described in Case Example #8 and illustrated in FIG. 6.

Microstructural changes in Alloy 1 at the shear edge as a result of the punching and annealing at different temperatures were examined by SEM. Cross section samples were cut from ASTM E8 punched tensile specimens near the sheared edge in as-punched condition and after annealing at 650° C. and 700° C. as shown in FIG. 48.

For SEM study, the cross section samples were ground on SiC abrasive papers with reduced grit size, and then polished progressively with diamond media paste down to 1 μm. The final polishing was done with 0.02 μm grit SiO2 solution. Microstructures were examined by SEM using an EVO-MA10 scanning electron microscope manufactured by Carl Zeiss SMT Inc.

FIG. 49 shows the backscattered SEM images of the microstructure at the edge in the as-punched condition. It can be seen that the microstructure is deformed and transformed in the shear affected zone (i.e., the triangle with white contrast close to the edge) in contrast to the recrystallized microstructure in the area away from the shear affected zone. Similar to tensile deformation, the deformation in the shear affected zone caused by punching creates Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) through Nanophase Refinement & Strengthening mechanism. However, annealing recovers the tensile properties of punched ASTM E8 specimens, which are related to the microstructure change in the shear affected zone during annealing. FIG. 50 shows the microstructure of the sample annealed at 650° C. for 10 minutes. Compared to the as-punched sample, the shear affected zone becomes smaller with less contrast suggesting that the microstructure in the shear affected zone evolves toward that in the center of the sample. A high magnification SEM image shows that some very small grains are nucleated, but recrystallization does not take place massively across the shear affected zone. It is likely that the recrystallization is in the early stage with most of the dislocations annihilated. Although the structure is not fully recrystallized, the tensile property is substantially recovered (Table 32 and FIG. 47a ). Annealing at 700° C. for 10 minutes leads to full recrystallization of the shear affected zone. As shown in FIG. 51, the contrast in shear affected zone significantly decreased. High magnification image shows that equiaxed grains with clear grain boundaries are formed in the shear affected zone, indicating full recrystallization. The grain size is smaller than that in the center of sample. Note that the grains in the center are resulted from recrystallization after annealing at 850° C. for 10 minutes before punching of specimens. With the shear affected zone fully recrystallized, the tensile properties are fully recovered, as shown in Table 32 and FIG. 47a .

Punching of tensile specimens result in edge damage lowering the tensile properties of the material. Plastic deformation of the sheet alloys herein during punching leads to structural transformation to a Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) with reduced ductility leading to premature cracking at the edge. This Case Example demonstrates that this edge damage is partially/fully recoverable by different anneals over a wide range of industrial temperatures.

TABLE 33 Tensile Properties after Punching and Annealing at Different Temperatures Ultimate Anneal Yield Tensile Tensile Temperature Strength Strength Elongation Alloy (° C.) (MPa) (MPa) (%) Alloy 1 As Punched 494 798 12.6 487 829 14.3 474 792 15.3 450 481 937 21.5 469 934 20.9 485 852 19.3 600 464 1055 27.3 472 1103 30.5 453 984 23.7 650 442 1281 51.5 454 1270 45.4 445 1264 51.1 700 436 1255 50.1 442 1277 52.1 462 1298 51.6 850 407 1248 52.0 406 1260 47.8 412 1258 48.5 Alloy 9 As Punched 508 1018 29.2 507 1007 28.6 490 945 23.3 600 461 992 28.5 462 942 24.8 471 968 25.6 650 460 1055 33.0 470 1166 48.3 473 1177 49.3 700 457 1208 57.5 455 1169 50.3 454 1171 61.6 850 411 1166 59.0 409 1174 52.7 418 1181 55.6 Alloy 12 As Punched 521 954 27.1 468 978 30.7 506 975 31.2 600 462 1067 44.9 446 1013 41.3 471 1053 41.1 650 452 1093 61.5 449 1126 57.8 505 1123 55.4 700 480 1112 59.6 460 1117 61.8 468 1096 61.5 850 419 1086 65.7 423 1085 63.0 415 1100 53.8

Case Example #10 Effect of Punching Speed on Punched Edge Property Reversibility

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 34 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to demonstrate edge damage recovery as a function of punching speed.

Tensile specimens in the ASTM E8 geometry were prepared by punching at three different speeds of 28 mm/s, 114 mm/s, and 228 min/s. Wire EDM cut specimens from the same materials were used for the reference. A part of punched tensile specimens from selected alloys was then put through a recovery anneal for 10 minutes at 850° C., followed by an air cool. Tensile properties were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.012 min/s. Strain data was collected using Instron's Advanced Video Extensometer. Tensile testing results are listed in Table 34 and tensile properties as a function of punching speed for selected alloys are illustrated in FIG. 52. It is seen that tensile properties drop significantly in the punched samples as compared to that for wire EDM cut. Punching speed increase from 28 mm/s to 228 min/s leads to increase in properties of all three selected alloys. The localized heat generation during punching a hole or shearing an edge is known to increase with increasing punching velocity and might be a factor in edge damage recovery in specimens punched at higher speed. Note that heat alone will not cause edge damage recovery but will be enabled by the materials response to the heat generated. This difference in response for the alloys contained in Table 2 in this application to commercial steel samples is clearly illustrated in Case Examples 15 and 17.

TABLE 34 Tensile Properties of Specimens Punched at Different Speed vs EDM Cut Sample Yield Tensile Tensile Preparation Strength Strength Elongation Alloy Method (MPa) (MPa) (%) Alloy 1 EDM 459 1255 51.2 443 1271 46.4 441 1248 52.7 453 1251 55.0 467 1259 51.3 228 mm/s Punched 474 952 21.8 498 941 21.6 493 956 21.6 114 mm/s Punched 494 798 13.4 487 829 15.1 474 792 14.1  28 mm/s Punched 464 770 12.8 479 797 13.7 465 755 12.1 Alloy 9 EDM 468 1166 56.1 480 1177 52.4 475 1169 56.9 228 mm/s Punched 500 1067 35.1 493 999 28.8 470 1042 31.8 114 mm/s Punched 508 1018 29.2 507 1007 28.6 490 945 23.3  28 mm/s Punched 473 851 19.7 472 841 16.4 494 846 18.9 Alloy 12 EDM 481 1094 54.4 479 1128 64.7 495 1126 62.4 228 mm/s Punched 495 1124 53.8 484 1123 53.0 114 mm/s Punched 521 954 27.1 468 978 30.7 506 975 31.2  28 mm/s Punched 488 912 23.6 472 900 21.7 507 928 22.9

This Case Example demonstrates that punching speed can have a significant effect on the resulting tensile properties in steel alloys herein. Localized heat generation at punching might be a factor in recovery of the structure near the edge leading to property improvement.

Case Example #11 Edge Structure Transformation During Hole Punching and Expansion

Slabs with thickness of 50 mm were laboratory cast from Alloy 1 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used for hole expansion ratio (HER) tests.

Specimens for testing with a size of 89×89 mm were wire EDM cut from the sheet. The hole with 10 mm diameter was cut in the middle of specimens by utilizing two methods: punching and drilling with edge milling. The hole punching was done on an Instron Model 5985 Universal Testing System using a fixed speed of 0.25 mm/s with 16% clearance. Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation. The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Results of HER testing are shown in FIG. 53 demonstrating a significantly lower value for the sample when the hole was prepared by punching as compared to milling: 5.1% HER vs 73.6% HER, respectively. Samples were cut from both tested samples as shown in FIG. 54 for SEM analysis and microhardness measurements.

Microhardness was measured for Alloy 1 at all relevant stages of the hole expansion process. Microhardness measurements were taken along cross sections of sheet samples in the annealed (before punching and HER testing), as-punched, and HER tested conditions. Microhardness was also measured in cold rolled sheet from Alloy 1 for reference. Measurement profiles started at an 80 micron distance from the edge of the sample, with an additional measurement taken every 120 microns until 10 such measurements were taken. After that point, further measurements were taken every 500 microns, until at least 5 mm of total sample length had been measured. A schematic illustration of microhardness measurement locations in HER tested samples is shown in FIG. 55. SEM images of the punched and HER tested samples after microhardness measurements are shown in FIG. 56.

As shown in FIG. 57, the punching process creates a transformed zone of approximately 500 microns immediately adjacent to the punched edge, with the material closest to the punched edge either fully or near-fully transformed, as evidenced by the hardness approaching that observed in the fully-transformed, 40% cold rolled material immediately next to the punched edge. Microhardness profiles for each sample is presented in FIG. 58. As it can be seen, microhardness gradually increases towards a hole edge in the case of milled while in the case of punched hole microhardness increase was observed in a very narrow area close to the hole edge. TEM samples were cut at the same distance in both cases as indicated in FIG. 58.

To prepare the TEM specimens, the HER test samples were first sectioned by wire EDM, and a piece with a portion of hole edge was thinned by grinding with pads of reduced grit size. Further thinning to ˜60 μm thickness is done by polishing with 9 μm, 3 μm, and 1 μm diamond suspension solution respectively. Discs of 3 mm in diameter were punched from the foils near the edge of the hole and the final polishing was completed by electropolishing using a twin-jet polisher. The chemical solution used was a 30% Nitric acid mixed in Methanol base. In case of insufficient thin area for TEM observation, the TEM specimens may be ion-milled using a Gatan Precision Ion Polishing System (PIPS). The ion-milling usually is done at 4.5 keV, and the inclination angle is reduced from 4° to 2° to open up the thin area. The TEM studies were done using a JEOL 2100 high-resolution microscope operated at 200 kV. Since the location for TEM study is at the center of the disc, the observed microstructure is approximately ˜1.5 mm from the edge of hole.

The initial microstructure of the Alloy 1 sheet before testing is shown on FIG. 59 representing Recrystallized Modal Structure (Structure #4, FIG. 1B). FIG. 60a shows the TEM micrograph of the microstructure in the HER test sample with punched hole after testing (HER=5.1%) in different areas at the location of 1.5 mm from hole edge. It was found that mainly the recrystallized microstructure remains in the sample (FIG. 60a ) with small amount of area with partially transformed “pockets” (FIG. 60b ) indicating that limited volume (˜1500 μm deep) of the sample was involved in deformation at HER testing. In the HER sample with milled hole (HER=73.6%), as shown in FIG. 61, there is a great amount of deformation in the sample as indicated by a large amount of transformed “pockets” and high density of dislocations (10⁸ to 10¹⁰ mm²).

To analyze in more detail the reason causing the poor HER performance in samples with punched holes, Focused Ion Beam (FIB) technique was utilized to make TEM specimens at the very edge of the punched hole. As shown in FIG. 62, TEM specimen is cut at ˜10 μm from the edge. To prepare TEM specimens by FIB, a thin layer of platinum is deposited on the area to protect the specimen to be cut. A wedge specimen is then cut out and lifted by a tungsten needle. Further ion milling is performed to thin the specimen. Finally the thinned specimen is transferred and welded to copper grid for TEM observation. FIG. 63 shows the microstructure of the Alloy 1 sheet at the distance of ˜10 micron from the punched hole edge which is significantly refined and transformed as compared to the microstructure in the Alloy 1 sheet before punching. It suggests that punching caused severe deformation at the hole edge such that Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B) occurred leading to formation of Refined High Strength Nanomodal Structure (Structure 45, FIG. 1B) in the area close to the punched hole edge. This structure has relative lower ductility as compared to Recrystallized Modal Structure Table 1 resulting in premature cracking at the edge and low HER values. This Case Example demonstrates that the alloys in Table 2 exhibit the unique ability to transform from a Recrystallized Modal Structure (Structure #4, FIG. 1B) to a Refined High Strength Nanomodal Structure (Structure #5, FIG. 1B) through the identified Nanophase Refinement & Strengthening (Mechanism #4, FIG. 1B). The structural transformation occurring due to deformation at the hole edge at punching appears to be similar in nature to transformation occurring during cold rolling deformation and that observed during tensile testing deformation.

Case Example #12 HER Testing Results With and Without Annealing

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 35 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used for hole expansion ratio (HER) tests.

Test specimens of 89×89 mm were wire EDM cut from the sheet from larger sections. A 10 mm diameter hole was made in the center of specimens by punching on an Instron Model 5985 Universal Testing System using a fixed speed of 0.25 mm/s at 16% punch to die clearance. Half of the prepared specimens with punched holes were individually wrapped in stainless steel foil and annealed at 850° C. for 10 minutes before HER testing. Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

.The results of the hole expansion ratio measurements on the specimens with and without annealing after hole punching are shown in Table 35. As shown in FIG. 64, FIG. 65, FIG. 66, FIG. 67 and FIG. 68 for Alloy 1, Alloy 9, Alloy 12, Alloy 13, and Alloy 17, respectively, the hole expansion ratio measured with punched holes with annealing is generally greater than in punched holes without annealing. The increase in hole expansion ratio with annealing for the identified alloys herein therefore leads to an increase in the actual HER of about 25% to 90%.

TABLE 35 Hole Expansion Ratio Results for Select Alloys With and Without Annealing Measured Average Hole Hole Punch Expansion Expansion Clearance Ratio Ratio Material Condition (%) (%) (%) Alloy 1 Without 16 3.00 3.20 Annealing 3.90 2.70 With 16 105.89 93.10 Annealing 81.32 92.11 Alloy 9 Without 16 3.09 3.19 Annealing 3.19 3.29 With 16 78.52 87.84 Annealing 97.60 87.40 Alloy 12 Without 16 4.61 4.91 Annealing 5.21 With 16 69.11 77.60 Annealing 83.60 80.08 Alloy 13 Without 16 1.70 1.53 Annealing 1.40 1.50 With 16 32.37 31.12 Annealing 29.00 32.00 Alloy 17 Without 16 12.89 21.46 Annealing 28.70 22.80 With 16 104.21 103.74 Annealing 80.42 126.58

This Case Example demonstrates that edge formability demonstrated during HER testing can yield poor results due to edge damage during the punching operation as a result of the unique mechanisms in the alloys listed in Table 2. The fully post processed alloys exhibit very high tensile ductility as shown in Table 6 through Table 10 coupled with very high strain hardening and resistance to necking until near failure. Thus, the material resists catastrophic failure to a great extent but during punching, artificial catastrophic failure is forced to occur near the punched edge. Due to the unique reversibility of the identified mechanisms, this deleterious edge damage as a result of Nanophase Refinement & Strengthening (Mechanism #3, FIG. 1A) and structural transformation can be reversed by annealing resulting in high HER results. Thus, high hole expansion ratio values can be obtained in a case of punching hole with following annealing and retaining exceptional combinations of tensile properties and the associated bulk formability.

In addition, it can be appreciated that the alloys herein that have undergone the processing pathways to provide such alloys in the form of Structure #4 (Recrystallized Modal Structure) will indicate, for a hole that is formed by shearing, and including a sheared edge, a first hole expansion ratio (HER₁) and upon heating the alloy will have a second hole expansion ratio (HER₂), wherein HER₂>HER₁.

More specifically, it can also be appreciated that the alloys herein that have undergone the processing pathways to provide such alloys with Structure #4 (Recrystallized Modal Structure) will indicate, for a hole that was placed in the alloy through methods (i.e. waterjet cutting, laser cutting, wire-edm, milling etc.) where the hole that is formed that does not rely primarily on shearing, compared to punching a hole, a first hole expansion ratio (HER₁) where such value may itself fall in the range of 30 to 130%. However, when the same alloy includes a hole formed by shearing, a second hole expansion ratio is observed (HER₂) wherein HER₂=(0.01 to 0.30)(HER₁). However, if the alloy is then subject to heat treatment herein, it is observed that HER₂ is recovered to a HER₃=(0.60 to 1.0) HER₁.

Case Example #13 Edge Condition Effect on Alloy Properties

Slabs with thickness of 50 mm were laboratory cast from Alloy 1 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from Alloy 1 with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to demonstrate the effect that edge condition has on Alloy 1 tensile and hole expansion properties.

Tensile specimens of AS TM E8 geometry were created using two methods: Punching and wire EDM cutting. Punched tensile specimens were created using a commercial press. A subset of punched tensile specimens was heat treated at 850° C. for 10 minutes to create samples with a punched then annealed edge condition.

Tensile properties of ASTM E8 specimens were measured on an Instron 5984 mechanical testing frame using Instron's Bluehill 3 control software. All tests were conducted at room temperature, with the bottom grip fixed and the top grip set to travel upwards at a rate of 0.025 mm/s for the first 0.5% elongation, and at a rate of 0.125 mm/s after that point. Strain data was collected using Instron's Advanced Video Extensometer. Tensile properties of Alloy 1 with punched, EDM cut, and punched then annealed edge conditions are shown in Table 36. Tensile properties of Alloy 1 with different edge conditions are shown in FIG. 69.

TABLE 36 Tensile Properties of Alloy 1 with Different Edge Conditions Ultimate Tensile Tensile Edge Elongation Strength Condition (%) (MPa) Punched 12.6 798 14.3 829 15.3 792 EDM Cut 50.5 1252 51.2 1255 52.7 1248 55.0 1251 51.3 1259 50.5 1265 Punched 52.0 1248 Then 47.8 1260 Annealed 48.5 1258

Specimens for hole expansion ratio testing with a size of 89×89 mm were wire EDM cut from the sheet. The holes with 10 mm diameter were prepared by two methods: punching and cutting by wire EDM. The punched holes with 10 mm diameter were created by punching at 0.25 mm/s on an Instron 5985 Universal Testing System with a 16% punch clearance and with using the flat punch profile geometry. A subset of punched samples for hole expansion testing were annealed with an 850° C. for 10 minutes heat treatment after punching.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Hole expansion ratio testing results are shown in Table 37. An average hole expansion ratio value for each edge condition is also shown. The average hole expansion ratio for each edge condition is plotted in FIG. 70. It can be seen that for samples with EDM cut and punched then annealed edge conditions the edge formability (i.e. HER response) is excellent, whereas samples with holes in the punched edge condition have considerably lower edge formability.

TABLE 37 Hole Expansion Ratio of Alloy 1 with Different Edge Conditions Measured Average Hole Hole Expansion Expansion Edge Ratio Ratio Condition (%) (%) Punched 3.00 3.20 3.90 2.70 EDM Cut 92.88 82.43 67.94 86.47 Punched 105.90 93.10 Then 81.30 Annealed 92.10

This Case Example demonstrates that the edge condition of Alloy 1 has a distinct effect on the tensile properties and edge formability (i.e. HER response). Tensile samples tested with punched edge condition have diminished properties when compared to both wire EDM cut and punched after subsequent annealing. Samples having the punched edge condition have hole expansion ratios averaging 3.20%, whereas EDM cut and punched then annealed edge conditions have hole expansion ratios of 82.43% and 93.10%, respectively. Comparison of edge conditions also demonstrates that damage associated with edge creation (i.e. via punching) has a non-trivial effect on the edge formability of the alloys herein.

Case Example #14 HER Results as a Function of Hole Punching Speed

Slabs with thickness of 50 mm were laboratory cast from selected alloys listed in Table 38 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) were used to demonstrate an effect of hole punching speed on HER results.

Specimens for testing with a size of 89×89 mm were wire EDM cut from the sheet. The holes with 10 mm diameter were punched at different speeds on two different machines but all of the specimens were punched with a 16% punch clearance and with the same punch profile geometry. The low speed punched holes (0.25 mm/s, 8 mm/s) were punched using an Instron 5985 Universal Testing System and the high speed punched holes (28 mm/s, 114 mm/s, 228 mm/s) were punched on a commercial punch press. All holes were punched using a flat punch geometry.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Hole expansion ratio values for tests are shown in Table 37. An average hole expansion value is shown for each speed and alloy tested at 16% punch clearance. The average hole expansion ratio as a function of punch speed is shown in FIG. 71, FIG. 72 and FIG. 73 for Alloy 1, Alloy 9, and Alloy 12, respectively. It can be seen that as punch speed increases, all alloys tested had a positive edge formability response, as demonstrated by an increase in hole expansion ratio. The reason for this increase is believed to be related to the following effects. With higher punch speed, the amount of heat generated at the sheared edge is expected to increase and the localized temperature spike may result in an annealing effect (i.e. in-situ annealing). Alternatively, with increasing punch speed, there may be a reduced amount of material transforming from the Recrystallized Modal Structure (i.e. Structure #4 in FIG. 1B) to the Refined High Strength Nanomodal Structure (i.e. Structure #5 in FIG. 1B). Concurrently, the amount of Refined High Strength Nanomodal Structure (i.e. Structure #5 in FIG. 1B) may be reduced due to the temperature spike enabling localized recrystallization (i.e. Mechanism #3 in FIG. 1B).

TABLE 38 Hole Expansion Ratio at Different Punch Speeds Measured Average Hole Hole Punch Expansion Expansion Speed Ratio Ratio Material (mm/s) (%) (%) Alloy 1 0.25 3.00 3.20 0.25 3.90 0.25 2.70 8 4.49 3.82 8 3.49 8 3.49 28 8.18 7.74 28 8.08 28 6.97 114 17.03 17.53 114 19.62 114 15.94 228 20.44 21.70 228 21.24 228 23.41 Alloy 9 0.25 3.09 3.19 0.25 3.19 0.25 3.29 8 6.80 6.93 8 7.39 8 6.59 28 21.04 19.11 28 17.35 28 18.94 114 24.80 24.29 114 19.74 114 28.34 228 26.00 30.57 228 35.16 228 30.55 Alloy 12 0.25 4.61 4.91 0.25 5.21 8 7.62 11.28 8 14.61 8 11.62 28 29.38 31.59 28 33.70 28 31.70 114 40.08 45.50 114 48.11 114 48.31 228 50.00 49.36 228 40.56 228 57.51

This Case Example demonstrates a dependence of edge formability on punching speed as measured by the hole expansion ratio. As punch speed increases, the hole expansion ratio generally increases for the alloys tested. With increased punching speed, the nature of the edge is changed such that improved edge formability (i.e. HER response) is achieved. At punching speeds greater than those measured, edge formability is expected to continue improving towards even higher hole expansion ratio values.

Case Example #15 HER in DP980 as a Function of Hole Punching Speed

Commercially produced and processed Dual Phase 980 steel was purchased and hole expansion ratio testing was performed. All specimens were tested in the as received (commercially processed) condition.

Specimens for testing with a size of 89×89 mm were wire EDM cut from the sheet. The holes with 10 mm diameter were punched at different speeds on two different machines but all of the specimens were punched with a 16% punch clearance and with the same punch profile geometry using a commercial punch press. The low speed punched holes (0.25 min/s) were punched using an Instron 5985 Universal Testing System and the high speed punched holes (28 mm/s, 114 mm/s, 228 min/s) were punched on a commercial punch press. All holes were punched using a flat punch geometry.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Values for hole expansion tests are shown in Table 39. The average hole expansion value for each punching speed is also shown for commercial Dual Phase 980 material at 16% punch clearance. The average hole expansion value is plotted as a function of punching speed for commercial Dual Phase 980 steel in FIG. 74.

TABLE 39 Hole Expansion Ratio of Dual Phase 980 Steel at Different Punch Speeds Measured Average Hole Hole Punch Expansion Expansion Speed Ratio Ratio Material (mm/s) (%) (%) Commercial Dual 0.25 23.55 22.45 Phase 980 0.25 20.96 0.25 22.85 28 18.95 18.26 28 17.63 28 18.21 114 17.40 20.09 114 23.66 114 19.22 228 27.21 23.83 228 24.30 228 19.98

This Case Example demonstrates that no edge performance effect based on punch speed is measureable in Dual Phase 980 steel. For all punch speeds measured on Dual Phase 980 steel the edge performance (i.e. HER response) is consistently within the 21%±3% range, indicating that edge performance in conventional AHSS is not improved by punch speed as expected since the unique structures and mechanisms present in this application as for example in FIGS. 1a and 1b are not present.

Case Example #16 HER Results as a Function of Punch Design

Slabs with thickness of 50 mm were laboratory cast from Alloys 1, 9, and 12 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Resultant sheet from each alloy with final thickness of 1.2 mm and Recrystallized Modal Structure (Structure #4, FIG. 1B) was used to demonstrate an effect of hole punching speed on HER results.

Tested specimens of 89×89 mm were wire EDM cut from larger sections. A 10 mm diameter hole was punched in the center of the specimen at three different speeds, 28 mm/s, 114 min/s, and 228 mm/s at 16% punch clearance and with four punch profile geometries using a commercial punch press. These punch geometries used were flat, 6° tapered, 7° conical, and conical flat. Schematic drawings of the 6° tapered, 7° conical, and conical flat punch geometries are shown in FIG. 75.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Hole expansion ratio data is included respectively in Table 40, Table 41, and Table 42 for Alloy 1, Alloy 9, and Alloy 12 at four punch geometries and at two different punch speeds. The average hole expansion values for Alloy 1, Alloy 9, and Alloy 12 are shown in FIG. 76, FIG. 77 and FIG. 78, respectively. For all alloys tested, the 7° conical punch geometry resulted in the largest or tied for the largest hole expansion ratio compared to all other punch geometries. Increased punch speed is also shown to improve the edge formability (i.e. HER response) for all punch geometries. At increased punching speed with different punch geometries, the alloys herein may be able to undergo some amount of Recrystallization (Mechanism #3) as it is contemplated that there could be localized heating at the edge at such higher relative punch speeds, triggering Mechanism #3 and formation of some amount of Structure #4.

TABLE 40 Hole Expansion Ratio of Alloy 1 with Different Punch Geometries Measured Average Hole Hole Punch Expansion Expansion Punch Speed Ratio Ratio Geometry (mm/s) (%) (%) Flat 28 8.18 7.74 Flat 28 8.08 Flat 28 6.97 Flat 114 17.03 17.53 Flat 114 19.62 Flat 114 15.94 Flat 228 20.44 21.70 Flat 228 21.24 Flat 228 23.41 6° Taper 28 7.87 8.32 6° Taper 28 8.77 6° Taper 114 19.84 18.48 6° Taper 114 16.55 6° Taper 114 19.04 7° Conical 28 8.37 10.56 7° Conical 28 12.05 7° Conical 28 11.25 7° Conical 114 23.41 22.85 7° Conical 114 21.14 7° Conical 114 24.00 7° Conical 228 21.71 21.37 7° Conical 228 19.50 7° Conical 228 22.91 Conical Flat 28 8.47 11.95 Conical Flat 28 13.25 Conical Flat 28 14.14 Conical Flat 114 20.42 19.75 Conical Flat 114 19.22 Conical Flat 114 19.62 Conical Flat 228 24.13 22.39 Conical Flat 228 23.31 Conical Flat 228 19.72

TABLE 41 Hole Expansion Ratio of Alloy 9 with Different Punch Geometries Measured Average Hole Hole Punch Expansion Expansion Punch Speed Ratio Ratio Geometry (mm/s) (%) (%) Flat 28 21.04 19.11 Flat 28 17.35 Flat 28 18.94 Flat 114 24.80 24.29 Flat 114 19.74 Flat 114 28.34 Flat 228 26.00 30.57 Flat 228 35.16 Flat 228 30.55 6° Taper 28 17.35 19.36 6° Taper 28 19.06 6° Taper 28 21.66 6° Taper 114 29.64 31.14 6° Taper 114 32.14 6° Taper 114 31.64 7° Conical 28 22.63 24.05 7° Conical 28 23.61 7° Conical 28 25.92 7° Conical 114 34.36 32.60 7° Conical 114 31.67 7° Conical 114 31.77 7° Conical 228 36.28 36.44 7° Conical 228 38.87 7° Conical 228 34.16 Conical Flat 28 27.72 25.59 Conical Flat 28 24.63 Conical Flat 28 24.43 Conical Flat 114 30.28 32.64 Conical Flat 114 32.87 Conical Flat 114 34.76 Conical Flat 228 32.90 35.45 Conical Flat 228 37.45 Conical Flat 228 35.99

TABLE 42 Hole Expansion Ratio of Alloy 12 with Different Punch Geometries Measured Average Hole Hole Punch Expansion Expansion Punch Speed Ratio Ratio Geometry (mm/s) (%) (%) Flat 28 29.38 31.59 Flat 28 33.70 Flat 28 31.70 Flat 114 40.08 45.50 Flat 114 48.11 Flat 114 48.31 Flat 228 50.00 49.36 Flat 228 40.56 Flat 228 57.51 6° Taper 28 29.91 30.67 6° Taper 28 32.50 6° Taper 28 29.61 6° Taper 114 38.42 41.19 6° Taper 114 44.37 6° Taper 114 40.78 7° Conical 28 34.90 33.76 7° Conical 28 33.00 7° Conical 28 33.37 7° Conical 114 45.72 49.10 7° Conical 114 49.30 7° Conical 114 52.29 7° Conical 228 58.90 54.36 7° Conical 228 53.43 7° Conical 228 50.75 Conical Flat 28 37.15 34.43 Conical Flat 28 31.47 Conical Flat 28 34.66 Conical Flat 114 45.76 46.36 Conical Flat 114 45.96 Conical Flat 114 47.36 Conical Flat 228 57.51 54.11 Conical Flat 228 53.48 Conical Flat 228 51.34

This Case Example demonstrates that for all alloys tested, there is an effect of punch geometry on edge formability. For all alloys tested, the conical punch shapes resulted in the largest hole expansion ratios, thereby demonstrating that modifying the punch geometry from a flat punch to a conical punch shape reduces the damage within the material due to the punched edge and improves edge formability. The 7° conical punch geometry resulted in the greatest edge formability increase overall when compared to the flat punch geometry with the conical flat geometry producing slightly lower hole expansion ratios across the majority of alloys tested. For Alloy 1 the effect of punch geometry is diminished with increasing punching speed, with the three tested geometries resulting in nearly equal edge formability as measured by hole expansion ratio (FIG. 79). Punch geometry, coupled with increased punch speeds have been demonstrated to greatly reduce residual damage from punching within the edge of the material, thereby improving edge formability. With higher punch speed, the amount of heat generated at the sheared edge is expected to increase and the localized temperature spike may result in an annealing effect (i.e. in-situ annealing). Alternatively, with increasing punch speed, there may be a reduced amount of material transforming from the Recrystallized Modal Structure (i.e. Structure #4 in FIG. 1B) to the Refined High Strength Nanomodal Structure (i.e. Structure #5 in FIG. 1B). Concurrently, the amount of Refined High Strength Nanomodal Structure (i.e. Structure #5 in FIG. 1B) may be reduced due to the temperature spike enabling localized recrystallization (i.e. Mechanism #3 in FIG. 1B).

Case Example #17 HER in Commercial Steel Grades as a Function of Hole Punching Speed

Hole expansion ratio testing was performed on commercial steel grades 780, 980 and 1180. All specimens were tested in the as received (commercially processed) sheet condition.

Specimens for testing with a size of 89×89 mm were wire EDM cut from the sheet of each grade. The holes with 10 mm diameter were punched at different speeds on two different machines with the same punch profile geometry using a commercial punch press. The low speed punched holes (0.25 mm/s) were punched using an Instron 5985 Universal Testing System at 12% clearance and the high speed punched holes (28 mm/s, 114 mm/s, 228 mm/s) were punched on a commercial punch press at 16% clearance. All holes were punched using a flat punch geometry.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Results from hole expansion tests are shown in Table 43 through Table 45 and illustrated in FIG. 80. As it can be seen, the hole expansion ratio does not show improvement with increasing punching speed in all tested grades.

TABLE 43 Hole Expansion Ratio of 780 Steel Grade at Different Punch Speeds Punch Punch to die Punch Sample Speed clearance Geo- # (mm/s) (%) metry HER 1  5 mm/s 12% Flat 44.74 2 12% Flat 39.42 3 12% Flat 44.57 1  28 mm/s 16% Flat 35.22 2 16% Flat 28.4 3 16% Flat 36.38 1 114 mm/s 16% Flat 31.58 2 16% Flat 33.9 3 16% Flat 22.29 1 228 mm/s 16% Flat 31.08 2 16% Flat 31.85 3 16% Flat 31.31

TABLE 44 Hole Expansion Ratio of 980 Steel Grade at Different Punch Speeds Punch Punch to die Punch Sample Speed clearance Geo- # (mm/s) (%) metry HER 1  5 mm/s 12% Flat 33.73 2 12% Flat 35.02 1  28 mm/s 16% Flat 26.88 2 16% Flat 26.44 3 16% Flat 23.83 1 114 mm/s 16% Flat 26.81 2 16% Flat 30.56 3 16% Flat 29.24 1 228 mm/s 16% Flat 30.06 2 16% Flat 30.98 3 16% Flat 30.62

TABLE 45 Hole Expansion Ratio of 1180 Steel Grade at Different Punch Speeds Punch Punch to die Punch Sample Speed clearance Geo- # (mm/s) (%) metry HER 1  5 mm/s 12% Flat 26.73 2 12% Flat 32.9 3 12% Flat 25.4 1  28 mm/s 16% Flat 35.32 2 16% Flat 32.11 3 16% Flat 36.37 1 114 mm/s 16% Flat 35.15 2 16% Flat 30.92 3 16% Flat 32.27 1 228 mm/s 16% Flat 27.25 2 16% Flat 23.98 3 16% Flat 31.18

This Case Example demonstrates that no edge performance effect based on hole punch speed is measureable in tested commercial steel grades indicating that edge performance in conventional AHSS is not effected or improved by punch speed as expected since the unique structures and mechanisms present in this application as for example in FIG. 1A and FIG. 1B are not present.

Case Example #18 Relationship of Post Uniform Elongation to Hole Expansion Ratio

Existing steel materials have been shown to exhibit a strong correlation of the measured hole expansion ratio and the material's post uniform elongation. The post uniform elongation of a material is defined as a difference between the total elongation of a sample during tensile testing and the uniform elongation, typically at the ultimate tensile strength during tensile testing. Uniaxial tensile testing and hole expansion ratio testing were completed on Alloy land Alloy 9 on the sheet material at approximately 1.2 mm thickness for comparison to existing material correlations.

Slabs with thickness of 50 mm were laboratory cast of Alloy 1 and Alloy 9 according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling annealing at 850° C. for 10 min as described in the Main Body section of this application.

Tensile specimens in the ASTM E8 geometry were prepared by wire EDM. All samples were tested in accordance with the standard testing procedure described in the Main Body of this document. An average of the uniform elongation and total elongation for each alloy were used to calculate the post uniform elongation. The average uniform elongation, average total elongation, and calculated post uniform elongation for Alloy 1 and Alloy 9 are provided in Table 46.

Specimens for hole expansion ratio testing with a size of 89×89 mm were wire EDM cut from the sheet of Alloy 1 and Alloy 9. Holes of 10 mm diameter were punched at 0.25 mm/s on an Instron 5985 Universal Testing System at 12% clearance. All holes were punched using a flat punch geometry. These test parameters were selected as they are commonly used by industry and academic professionals for hole expansion ratio testing.

Hole expansion ratio (HER) testing was performed on the SP-225 hydraulic press and consisted of slowly raising the conical punch that uniformly expanded the hole radially outward. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

The measured hole expansion ratio values for Alloy 1 and Alloy 9 are provided in Table 46.

TABLE 46 Uniaxial Tensile and Hole Expansion Data for Alloy 1 and Alloy 9 Post Average Average Uniform Hole Uniform Total Elongation Expansion Elongation Elongation (ε_(pul)) Ratio Alloy (%) (%) (%) (%) Alloy 1 47.19 49.29 2.10 2.30 Alloy 9 50.83 56.99 6.16 2.83

Commercial reference data is shown for comparison in Table 47 from [Paul S. K., J Mater Eng Perform 2014; 23:3610.]. For commercial data, S. K. Paul's prediction states that the hole expansion ratio of a material is proportional to 7.5 times the post uniform elongation (See Equation 1).

HER=7.5(ε_(pul))   Equation 1

TABLE 47 Reference Data from [Paul S.K., J Mater Eng Perform 2014;23:3610.] Post Uniform Hole Commercial Uniform Total Elongation Expansion Steel Elongation Elongation (ε_(pul)) Ratio Grade (%) (%) (%) (%) IF-Rephos 22 37.7 15.7 141.73 IF-Rephos 22.2 39.1 16.9 159.21 BH210 19.3 37.8 18.5 151.96 BH300 16.5 29 12.5 66.63 DP 500 18.9 27.5 8.6 55.97 DP 600 16.01 23.51 7.5 38.03 TRIP 590 22.933 31.533 8.6 68.4 TRIP 600 19.3 27.3 8 39.98 TWIP940 64 66.4 2.4 39.1 HSLA 350 19.1 30 10.9 86.58 340 R 22.57 36.3 13.73 97.5

The Alloy 1 and Alloy 9 post uniform elongation and hole expansion ratio are plotted in FIG. 81 with the commercial alloy data and S.K. Paul's predicted correlation. Note that the data for Alloy 1 and Alloy 9 do not follow the predicted correlation line.

This Case Example demonstrates that for the steel alloys herein, the correlation between post uniform elongation and the hole expansion ratio does not follow that for commercial steel grades. The measured hole expansion ratio for Alloy 1 and Alloy 9 is much smaller than the predicted values based on correlation for existing commercial steel grades indicating an effect of the unique structures and mechanisms are present in the steel alloys herein as for example shown in FIG. 1a and FIG. 1 b.

Case Example #19 HER Performance as a Function of Hole Expansion Speed

Slabs with thickness of 50 mm were laboratory cast from three selected alloys according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Sheet from each alloy possessing the Recrystallized Modal Structure with final thickness of 1.2 mm were used to demonstrate the effect of hole expansion speed on HER performance.

Specimens for testing with a size of 89×89 mm were cut via wire EDM from the sheet. Holes of 10 mm diameter were punched at a constant speed of 228 mm/s on a commercial punch press. All holes were punched with a flat punch geometry, and with approximately 16% punch to die clearance.

Hole expansion ratio (HER) testing was performed on an Interlaken Technologies SP-225 hydraulic press and consisted of raising the conical punch that uniformly expanded the hole radially outward. Four hole expansion speeds, synonymous with the conical ram travel speed, were used; 5, 25, 50, and 100 mm/min. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Hole expansion ratio values for the tests are shown in Table 48. The average hole expansion ratio value is shown for each speed and alloy tested showing an increase in HER values with increasing hole expansion speed in all three alloys. The effect of hole expansion speed is also demonstrated in FIG. 82, FIG. 83, and FIG. 84 for Alloy 1, Alloy 9, and Alloy 12, respectively.

TABLE 48 Hole Expansion Ratio in Selected Alloys at Different Expansion Speeds Measured Average Hole Hole Hole Punch Expansion Expansion Expansion Speed Speed Ratio Ratio Material (mm/s) (mm/min) (%) (%) Alloy 1 228 5 19.09 20.55 22.54 20.02 25 30.70 28.58 29.14 25.91 50 34.05 34.63 36.43 33.42 100 37.11 37.19 38.52 35.93 Alloy 9 228 5 34.06 34.15 34.07 34.31 25 32.87 40.77 45.46 43.98 50 38.39 44.17 39.71 54.42 100 48.01 49.50 55.27 45.23 Alloy 12 228 5 48.61 43.51 34.79 47.14 25 42.13 50.64 57.82 51.96 50 63.77 62.97 68.46 56.68 100 57.79 56.73 49.28 63.11

This Case Example demonstrates that formability of the edge, i.e. its ability to be deformed with relatively reduced cracking, as measured by HER testing, can be affected by the speed of deformation of the hole edge (i.e. hole expansion speed). The alloys tested in this Case Example demonstrated a positive correlation between hole expansion ratio and the hole expansion speed, with increasing hole expansion speed resulting in relatively higher measured hole expansion ratios.

Accordingly, in the broad context of the present disclosure, it has been established that once an edge is formed, of any geometry by any edge formation method which causes deformation of the metal alloy when forming the edge (e.g. by punching, shearing, piercing, perforating, cutting, cropping, stamping,), by increasing the speed at which that edge once formed is then expanded, one observes that the edge itself is then capable of more expansion with a relatively reduced tendency to crack. The edge herein can therefore include an edge that defines an internal hole in a metal sheet of the alloys described herein, or an external edge on such metal sheet. In addition, the edge herein may be formed in a progressive die stamping operation which is reference to metal working operation that typically includes punching, shearing, coining and bending. The edge herein may be present in a vehicle, or more specifically, part of a vehicular frame, vehicular chassis, or vehicle panel.

Reference to edge expansion herein is understood as increasing the length of such edge with a corresponding change in the thickness of the edge. That is confirmed by the above data in Table 48, which shows that with respect to an edge that is present in a hole, when such edge in the hole is expanded at a speed of greater than or equal to 5 min/min, one observes an increase in the hole expansion ratio (i.e. the edge in the hole is capable of expansion to higher percentages over the original diameter) and the edge getting thinner as shown for example in the cross sections of the expanded edges in FIG. 91.

Case Example 20 HER Performance as a Function of Punch Speed and Hole Expansion Speed

Sheet from Alloy 9 was produced according to the atomic ratios provided in Table 2. Slabs produced by continuous casting were hot rolled into hot band which was subsequently processed into sheet with thickness of approximately 1.4 mm by cold rolling and annealing cycles. The microstructure of the produced sheet using both SEM and etched optical microscopy is demonstrated in FIG. 85 showing typical Recrystallized Modal Structure.

In FIG. 85A and FIG. 85B, the SEM micrographs shows the micron scale nature of the austenitic grains which contain some annealing twins and stacking faults. In FIG. 85C and FIG. 85D, etched samples were examined using optical microscopy. It can be seen that the grain boundaries are preferentially etched and the microstructure showing the grain boundaries. The grain size was measured with the line intercept method and is found to range from 6 μm to 22 μm with a mean value of 15 μm.

The sheet with Recrystallized Modal Structure was used for HER testing. Specimens for testing with a size of 89×89 mm were cut via wire EDM from the sheet. Holes of 10 mm diameter were punched at two different speeds of 5 mm/s using an Instron mechanical test frame and at 228 mm/s using a commercial punch press with a flat punch geometry and with punch to die clearances of approximately 12.5% and 16%, respectively.

Hole expansion ratio (HER) testing was performed on an Interlaken Technologies SP-225 hydraulic press and consisted of raising the conical punch that uniformly expanded the hole radially outward. Two hole expansion speeds of 3 mm/min and 50 mm/min, synonymous with the conical ram travel speed, were used. A digital image camera system was focused on the conical punch and the edge of the hole was monitored for evidence of crack formation and propagation.

The initial diameter of the hole was measured twice with calipers, measurements were taken at 90° increments and averaged to get the initial hole diameter. The conical punch was raised continuously until a crack was observed propagating through the specimen thickness. At that point the test was stopped and the hole expansion ratio was calculated as a percentage of the initial hole diameter measured before the start of the test. After expansion four diameter measurements were taken using calipers every 45° and averaged to account for any asymmetry of the hole due to cracking.

Hole expansion ratio values for tests are listed in Table 49. HER values vary from 2.4 to 18.5% in the samples with holes punched at 5 mm/s. In the case of 228 mm/s hole punching speed, HER values are significantly higher in a range from 33.8 to 75.0%. The effect of expansion speed is illustrated in FIG. 86. Increase in expansion speed results in higher HER values independent of utilized punching speeds (i.e. 5 mm/s and 228 mm/s).

TABLE 49 Hole Expansion Ratio in Alloy 9 Sheet at Different Punching and Expansion Speeds Hole Hole Punch Punch Expansion Clearance Speed Speed HER (%) (mm/s) (mm/min) (%) 16 228 3 33.8 16 228 3 41.3 16 228 50 63.1 16 228 50 75.0 12.5 5 3 2.4 12.5 5 3 7.9 12.5 5 50 12.7 12.5 5 50 18.5

The magnetic phases volume percent (Fe %) was measured in the HER tested samples with different hole punching speed and hole expansion speed using a Fischer Feritscope FMP30. The results are listed in Table 50. FIG. 87 illustrates the effect of on the magnetic phases volume percent in the tested samples as a function of the distance from the hole edge. As can be seen with higher punch speed and/or higher expansion speed, after testing is completed, the magnetic phase volume % increases near the hole edge and also away from the hole edge into the material. As the increase in magnetic phase volume (Fe %) is consistent with increases in the amount of Structure #5 in Table 1 which is formed during deformation, due to the formation of magnetic nanoscale alpha-iron from the starting non-magnetic austenite present in Structure #4.

TABLE 50 Magnetic Phases Volume (Fe%) in Alloy 9 at Different Hole Punching Speeds and Hole Expansion Speeds as a Function of Distance from Hole Edge After Expansion Hole Creation and Expansion Parameters Hole Punching Speed 228 228 228 228 5 5 5 5 (mm/s) Punch Clearance (%) 16 16 16 16 12.5 12.5 12.5 12.5 Hole Expansion Speed 3 3 50 50 3 3 50 50 (mm/min) HER (%) 33.8 41.3 63.1 75.0 2.4 7.9 12.7 18.5 Distance from hole (mm) Magnetic Phases Volume % (Fe %) 1 27.3 31.6 37.9 39.1 7.1 9.5 13.5 20.1 2.5 17 21.1 29.6 36 2.4 2.7 6.5 6.2 4 6 7.5 17.4 24.6 0.94 1.1 2.4 2.4 5.5 2.2 2.8 6.3 11.3 0.47 0.45 0.96 0.75 7 0.82 0.89 2.8 4.4 0.21 0.29 0.38 0.28 8.5 0.33 0.35 1.3 1.9 0.23 0.22 0.24 0.16 10 0.21 0.21 0.66 1.1 0.21 0.2 0.2 0.13 11.5 0.15 0.16 0.42 0.67 0.2 0.18 0.21 0.12 13 0.13 0.14 0.26 0.37 0.18 0.18 0.22 0.11 14.5 0.12 0.13 0.25 0.31 0.19 0.18 0.23 0.11 16 0.13 0.14 0.31 0.38 0.19 0.19 0.22 0.13 17.5 0.2 0.22 0.53 0.84 0.19 0.2 0.24 0.14 19 0.16 0.25 0.37 0.61 0.2 0.22 0.22 0.12 22 0.11 0.13 0.21 0.24 0.19 0.21 0.22 0.1 25 0.12 0.12 0.19 0.23 0.19 0.2 0.2 0.11

This Case Example illustrates that the relative resistance to cracking of an edge as confirmed by HER testing can be increased by, in the exemplary case of forming an edge within a hole, by either increasing hole punching speeds, hole expansion speeds or both. The sheet from Alloy 9, tested in this Case Example, demonstrated an increase in hole expansion ratio with increasing hole punching speed (i.e. 5 to 228 mm/s) and/or the hole expansion speed (i.e. 3 to 50 mm/min). Accordingly, preferably herein for the subject alloys, one forms an edge in the alloy and expands the edge at a speed of greater than or equal to 5 mm/min. The magnetic phases volume percent (Fe %) in tested samples increases with increasing hole punching speed and/or the hole expansion speed over the ranges studied. With this relatively greater amount of deformation available in and adjacent to the hole edge during the now disclosed increased hole punching speed or hole expansion speed, the higher local formability and resistance to cracking of the edge is achieved in the material as measured by the HER.

Case Example #21 HER Performance as a Function of Hole Preparation Method

Slabs with thickness of 50 mm were laboratory cast from three selected alloys according to the atomic ratios provided in Table 2 and laboratory processed by hot rolling, cold rolling and annealing at 850° C. for 10 min as described herein. Sheet from each alloy possessing the Recrystallized Modal Structure with final thickness of 1.2 mm were used to demonstrate an effect of hole expansion speed on HER performance.

Specimens for testing with a size of 89×89 mm were cut via wire EDM from the sheet. A 10 mm diameter hole was prepared by various methods including punching, EDM cutting, milling, and laser cutting. Hole punching was done at a low quasistatic punching speed of 0.25 mm/s at 16% punch to die clearance using a Komatsu OBS80-3 press. EDM cut holes were first rough cut then the final cut was made at parameters to yield a visually smooth surface. During hole milling, holes were pilot drilled, reamed to size, and then deburred. Laser cut samples were cut on a 4 kW fiber optic Mazak Optiplex 4020 Fiber II machine.

Hole expansion ratio (HER) testing was performed on an Interlaken Technologies SP-225 hydraulic press and consisted of raising the conical punch that uniformly expanded the hole radially outward. In FIG. 88, the results of HER testing is provided for each alloy as a function of the hole preparation method. As shown, in the case of punched holes, HER values are the lowest for all three alloys in a range from 6 to 12%. Samples with EDM cut, milled and laser cut holes exhibit high HER values from 65 to 140%+. Note that the ˜140% expansion represented the maximum extension limit of the press crosshead during testing so, in the samples with EDM cut holes from Alloy 12, and with milled holes from Alloy 9 and Alloy 12, the expansion limit was not reached during HER testing (i.e. actual value >140%).

In FIG. 89, SEM images of the sample cross section near the hole edge prior to expansion are provided at low magnification for samples from Alloy 1 with holes prepared by different methods. In the punched sample (FIG. 89A), the typical rollover zone at the top and burr zone at the bottom can be seen. Additionally, a hemispherical shear affected zone is visible at the edge of the hole with penetration of ˜0.5 mm at the deepest point. A similarly shear affected zone was observed in punched samples from the other two alloys as well but not in any of the samples with holes produced by the non-punching methods. Note that every method utilized for hole preparation introduced some kind of defects at the hole edge. In the EDM cut hole (FIG. 89B), the edge is perpendicular on a cross section image but small micron scaled cutting defects can be seen at the surface; in the milled samples (FIG. 89C) the edge of the holes is trapezoidal in shape; and in the laser cut holes (FIG. 89D), the edge wandered in a sideways fashion as the laser penetrated the sample. In FIG. 90, SEM images of the cross sections near the hole edge (i.e. at the edge and up to 0.7 mm away from the edge) prior to expansion are provided at higher magnification for samples from Alloy 1 with holes prepared by different methods including punching at a hole punching speed of 0.25 mm/s, EDM cut hole, milled hole, and laser cut hole. The microstructure near the hole edges are illustrated in FIGS. 90A, 90B, 90C and 90D respectively. As can be seen, the edge of the hole punched at 0.25 mm/s (FIG. 90a ) is relatively highly deformed thereby leading to the observed low HER values. This structure near the edge of the punched sample is representative of Structure #5 Refined High Strength Nanomodal Structure in Table 1 whereby the structures near the hole edge of the EDM cut, milled, and laser cut holes, is representative of Structure #4 Recrystallized Modal Structure in Table 1. However, in examples where holes were prepared by non-punching methods (FIGS. 90B, 90C, 90D), the resulting alloys experienced excellent local formability with high HER values from 65 to 140%+ consistent with the ductile nature of Structure #4 near the hole edges. In FIG. 91A (punched hole), 91B (EDM cut hole), 92C (milled hole), and 91D (laser cut hole), SEM images of the cross section near the hole edge after HER testing are provided at low magnification for samples from Alloy 1. Note that the thickness of samples near the hole is smaller in the expanded samples with higher HER values since the expansion of the holes results in sample thinning near the hole edge.

In FIG. 92, images of sample cross sections near the hole edge after HER testing (i.e. after expansion until failure by cracking) are provided at higher magnification for samples from Alloy 1 with holes prepared by different methods showing similar deformed structure in all cases. Since hole expansion and deformation of the edge is complete, the microstructure near all of the hole edges are similiar and representative of Structure #5 Refined High Strength Nanomodal Structure in Table 1.This Case Example demonstrates the effect of edge preparation on the resulting local formability in alloys herein. Punching at a low speeds of 0.25 mm/s is causing structural changes near the hole edge consistent with previous case examples resulting in limited local formability of the edges and low HER values. However, in examples where holes were prepared by non-punching methods, the resulting alloys experienced excellent local formability with high HER values from 65 to 140%+ consistent with the ductile nature of the microstructure in the samples and at the hole edges. 

1. A cold rolled steel sheet product comprising Fe and at least four alloying elements selected from Si, Mn, B, Cr, Ni, Cu and C, wherein the steel sheet product includes a sheared edge, has an ultimate tensile strength of at least 799 MPa, a total elongation of at least 6.6 percent, and a hole expansion ratio greater than
 20. 2. The steel sheet product of claim 1, wherein the steel sheet product comprises at least five of the elements selected from Si, Mn, B, Cr, Bi, Cu and C.
 3. The steel sheet product of claim 1, wherein the steel sheet product comprises at least six of the elements selected from Si, Mn, B, Cr, Ni, Cu and C.
 4. The steel sheet product of claim 1, wherein the steel sheet product comprises Fe, Si, Mn, B, Cr, Ni, Cu and C.
 5. The steel sheet product of claim 1, wherein the steel sheet product has a yield strength of at least 400 MPa.
 6. The steel sheet product of claim 1, wherein the sheared edge comprises an internal hole and/or an external edge.
 7. The steel sheet product of claim 1, wherein the sheared edge is formed by punching, piercing, perforating, cutting, cropping, EDM cutting, waterjet cutting, laser cutting, or milling.
 8. The steel sheet product of claim 1, wherein the steel sheet product is annealed.
 9. The steel sheet product of claim 8, wherein the sheared edge has been subjected to annealing after formation of the sheared edge.
 10. The steel sheet product of claim 8, wherein the steel sheet product has been subjected to annealing prior to formation of the sheared edge.
 11. The steel sheet product of claim 1, wherein the sheared edge is formed in a progressive die stamping operation.
 12. The steel sheet product of claim 1, wherein the sheared edge of the steel sheet product is positioned in a vehicle.
 13. The steel sheet product of claim 1, wherein the sheared edge of the steel sheet product is part of a vehicular frame, vehicular chassis, or vehicular panel. 